BR112018011765B1 - EMULSIONS COMPRISING A SUN PROTECTION FACTOR UV AND A CARNOSINE COMPOUND, PROCESS FOR PRODUCTION OF SUNSCREEN IN EMULSION FORM, AND USE OF CARNOSINE COMPOUNDS - Google Patents
EMULSIONS COMPRISING A SUN PROTECTION FACTOR UV AND A CARNOSINE COMPOUND, PROCESS FOR PRODUCTION OF SUNSCREEN IN EMULSION FORM, AND USE OF CARNOSINE COMPOUNDS Download PDFInfo
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- BR112018011765B1 BR112018011765B1 BR112018011765-0A BR112018011765A BR112018011765B1 BR 112018011765 B1 BR112018011765 B1 BR 112018011765B1 BR 112018011765 A BR112018011765 A BR 112018011765A BR 112018011765 B1 BR112018011765 B1 BR 112018011765B1
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- Brazil
- Prior art keywords
- acid
- emulsions
- weight
- carnosine
- esters
- Prior art date
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- 239000000839 emulsion Substances 0.000 title claims abstract description 55
- 230000037072 sun protection Effects 0.000 title claims abstract description 34
- -1 CARNOSINE COMPOUND Chemical class 0.000 title claims description 113
- CQOVPNPJLQNMDC-ZETCQYMHSA-N carnosine Chemical class [NH3+]CCC(=O)N[C@H](C([O-])=O)CC1=CNC=N1 CQOVPNPJLQNMDC-ZETCQYMHSA-N 0.000 title claims description 36
- CQOVPNPJLQNMDC-UHFFFAOYSA-N N-beta-alanyl-L-histidine Natural products NCCC(=O)NC(C(O)=O)CC1=CN=CN1 CQOVPNPJLQNMDC-UHFFFAOYSA-N 0.000 title claims description 32
- 229940044199 carnosine Drugs 0.000 title claims description 32
- 108010087806 Carnosine Proteins 0.000 title claims description 31
- QRYRORQUOLYVBU-VBKZILBWSA-N Carnosic acid Natural products CC([C@@H]1CC2)(C)CCC[C@]1(C(O)=O)C1=C2C=C(C(C)C)C(O)=C1O QRYRORQUOLYVBU-VBKZILBWSA-N 0.000 title claims description 28
- 238000000034 method Methods 0.000 title claims description 19
- 239000000516 sunscreening agent Substances 0.000 title claims description 12
- 230000008569 process Effects 0.000 title claims description 11
- 230000000475 sunscreen effect Effects 0.000 title claims description 11
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 25
- 150000001875 compounds Chemical class 0.000 claims abstract description 22
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- 150000004665 fatty acids Chemical class 0.000 claims description 38
- 125000004432 carbon atom Chemical group C* 0.000 claims description 36
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 32
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical class OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 claims description 31
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Abstract
emulsões com fatores de proteção solar uv e carnosinas. a presente invenção refere-se a emulsões contendo (a) pelo menos um fator de proteção solar uv, (b) pelo menos um composto da fórmula (i), (i) em que r1 representa h ou ch3 e r2 representa h ou cooh ou seus sais; (c) pelo menos um emulsificante, bem como opcionalmente (d1) veículo e/ou (d) corpo oleoso com a condição, de que as emulsões apresentem um tamanho de gotícula, nas quais o valor d50 situe-se na faixa de 0,1 a 100 µm.emulsions with uv sun protection factors and carnosines. The present invention relates to emulsions containing (a) at least one UV sun protection factor, (b) at least one compound of formula (i), (i) wherein r1 represents h or ch3 and r2 represents h or cooh or its salts; (c) at least one emulsifier, as well as optionally (d1) vehicle and/or (d) oily body with the condition that the emulsions have a droplet size, in which the d50 value lies in the range of 0, 1 to 100 µm.
Description
[001] A invenção encontra-se no campo dos cosméticos e refere-se especialmente aos agentes de proteção solar em forma de emulsão com melhor estabilidade ao armazenamento.[001] The invention is in the field of cosmetics and refers especially to sunscreen agents in emulsion form with better storage stability.
[002] De acordo com uma estatística do ano de 2015, o número de pessoas acima de 14 anos na Alemanha, que aplicam produtos de proteção solar por mais de 20 dias ao ano, é de cerca de 20 milhões e durante os últimos anos está aumentando constantemente. Assim, os protetores solares são incluídos nos produtos cosméticos mais procurados, uma vez que de acordo com estudos atuais, o número de câncer de pele provocado pela radiação UV desde o ano de 2003 mais que dobrou.[002] According to a 2015 statistic, the number of people over 14 years old in Germany, who apply sun protection products for more than 20 days a year, is around 20 million and during the last few years it is constantly increasing. Thus, sunscreens are included in the most sought after cosmetic products, since according to current studies, the number of skin cancers caused by UV radiation since 2003 has more than doubled.
[003] Os protetores solares são muitos variados com respeito à composição, qualidade e, com isso, também, por fim, ao preço. Receitas simples, que são oferecidas principalmente por lojas de desconto, são constituídas de forma muito simples e contêm apenas poucos fatores de proteção solar em pequenas quantidades o que, na melhor das hipóteses, leva a uma proteção de curto prazo na pele previamente bronzeada. Outros produtos apresentam um “coquetel” de fatores de proteção solar, isto é, aqui é aproveitado, que os fatores de proteção solar têm sua absorção máxima em diferentes faixas de comprimento de onda e com escolha inteligente obtém-se, assim, uma proteção uniforme através de um amplo espectro da luz solar branca. É óbvio, que esses produtos não são apenas qualitativamente de alto valor, mas justamente também são mais caros para o consumidor.[003] Sunscreens are very varied with respect to composition, quality and, with that, also, finally, the price. Simple recipes, which are mainly offered by discount stores, are made very simply and contain only a few sun protection factors in small amounts which, at best, leads to short-term protection on previously tanned skin. Other products present a “cocktail” of sun protection factors, that is, here it is used that the sun protection factors have their maximum absorption in different wavelength ranges and, with an intelligent choice, uniform protection is obtained. through a broad spectrum of white sunlight. It is obvious, that these products are not only qualitatively of high value, but they are also more expensive for the consumer.
[004] Ininterrupta é a tendência, para melhorar os agentes cosméticos em seu efeito através da adição de outras substâncias ativas. No âmbito dos produtos de proteção solar há, por exemplo, um grande interesse em identificar as substâncias ativas, que estendem a área de proteção, isto é, não concedem apenas a proteção contra o dano da pele ou o envelhecimento da pele induzido pela luz (influência UV), mas também em relação a outras influências, tais como, por exemplo, toxinas ambientais. O fato é, a saber, que os fatores de proteção solar são amplamente ou mesmo completamente inúteis contra os danos da pele induzidos pelo meio ambiente, visto que esses seguem percursos de reação completamente diferentes na célula.[004] There is an unbroken tendency to improve cosmetic agents in their effect by adding other active substances. In the field of sun protection products, there is, for example, great interest in identifying active substances that extend the area of protection, i.e., they do not only provide protection against skin damage or light-induced skin aging ( UV influence), but also in relation to other influences such as, for example, environmental toxins. The fact is, namely, that sun protection factors are largely or even completely useless against environmentally induced skin damage, as these follow completely different reaction pathways in the cell.
[005] Com a introdução de substâncias ativas novas ou adicionais, contudo, não está associado apenas um aumento de qualidade, os problemas também crescem. Nem toda a substância ativa pode ser incorporada em cada formulação desejada, a complexidade na produção e armazenamento aumenta e sob certas circunstâncias também deve ser levado em conta, que o próprio aditivo é novamente sensível à influência do ar ou da luz.[005] With the introduction of new or additional active substances, however, it is not only associated with an increase in quality, the problems also grow. Not every active substance can be incorporated into every desired formulation, the complexity in production and storage increases and under certain circumstances it must also be taken into account that the additive itself is again sensitive to the influence of air or light.
[006] Particularmente interessante são as correspondentes pre parações em forma de emulsão, nas quais as gotículas apresentam um diâmetro particularmente pequeno, visto que essas não apenas podem ser facilmente atomizadas, mas também apresentam um alto poder de espalhamento, isto é, penetram rapidamente na pele. Tais emulsões caracterizam-se pelo fato, de que as gotículas são tão pequenas, que essas não espalham a luz. As soluções parecem, por conseguinte, ser transparentes. A desvantagem de tais formulações consiste, no entanto, em que no caso de um armazenamento mais longo e, em particular, a temperaturas elevadas, essas não apresentam uma estabilidade suficiente e, do mesmo modo, se desmisturam tão facilmente, como se formaram. Justamente essas são, porém, condições, às quais os protetores solares estão sujeitos regularmente.[006] Particularly interesting are the corresponding preparations in the form of an emulsion, in which the droplets have a particularly small diameter, since they can not only be atomized easily, but also have a high scattering power, that is, they quickly penetrate the surface. skin. Such emulsions are characterized by the fact that the droplets are so small that they do not scatter light. The solutions therefore appear to be transparent. The disadvantage of such formulations is, however, that in the case of a longer storage, and in particular at elevated temperatures, they do not show sufficient stability and, likewise, they unmix as easily as they were formed. However, these are precisely the conditions to which sunscreens are regularly subject.
[007] Em princípio, isso é inofensivo para o produto, visto que esse pode ser novamente homogeneizado através de múltiplas agitações vigorosas. Para um consumidor, que se decidiu justamente por um produto de alta qualidade e correspondentemente caro, porém, isso é insatisfatório e opcionalmente levará ao fato, de que próxima decisão de compra seja diferente.[007] In principle, this is harmless to the product, as it can be homogenized again through multiple vigorous shaking. For a consumer, who has just decided on a high-quality and correspondingly expensive product, however, this is unsatisfactory and will optionally lead to the fact that the next purchase decision will be different.
[008] O objetivo da presente consistiu, por conseguinte, em pôr à disposição protetores solares à base de emulsão, que também em um armazenamento prolongado de temperatura sejam suficientemente estáveis. Parte desse objetivo foi encontrar estabilizadores correspondentes, que de acordo com a possibilidade preencham não apenas um objetivo funcional, mas, além disso, também apresentem ainda um caráter de substância ativa, que é vantajoso para o campo de aplicação da proteção solar.[008] The objective of the present one was, therefore, to make available emulsion-based sunscreens, which, also in a prolonged temperature storage, are sufficiently stable. Part of this objective was to find corresponding stabilizers, which as possible fulfill not only a functional objective, but, in addition, also present an active substance character, which is advantageous for the field of application of sun protection.
[009] Um primeiro objeto da invenção refere-se às emulsões contendo (a) pelo menos um fator de proteção solar UV, (b) pelo menos um composto da fórmula (I) [009] A first object of the invention relates to emulsions containing (a) at least one UV sun protection factor, (b) at least one compound of formula (I)
[0010] na qual R1 representa H ou CH2 e R2 representa H ou COOH ou sais dos mesmos; (c) pelo menos um emulsificante e opcionalmente (d1) veículo e/ou (d2) substância oleosa[0010] in which R1 represents H or CH2 and R2 represents H or COOH or salts thereof; (c) at least one emulsifier and optionally (d1) vehicle and/or (d2) oily substance
[0011] com a condição, de que as emulsões apresentem um tamanho de gotícula, nas quais o valor D50 está na faixa de 0,1 a 100 μm, em particular, na faixa de 0,5 a 70 μm e de modo particularmente preferido, na faixa de 1 a 50 μm.[0011] with the proviso that the emulsions have a droplet size in which the D50 value is in the range of 0.1 to 100 μm, in particular in the range of 0.5 to 70 μm and particularly preferably , in the range of 1 to 50 μm.
[0012] A indicação significa, que pelo menos 50% de todas as go-tículas da emulsão estão na faixa de valor indicado. Além disso, é preferível, que o valor D90 esteja na faixa de na faixa de 1 a 150 μm e de modo particularmente preferido, na faixa de 10 a 100 μm. É particularmente preferível, que tanto o valor D50, quanto também o valor D90 situem-se na faixa de 0,1 a 100 μm e, em particular, na faixa de 1 a 40 μm.[0012] Indication means that at least 50% of all droplets in the emulsion are in the indicated value range. Furthermore, it is preferable that the D90 value is in the range of in the range of 1 to 150 μm and particularly preferably in the range of 10 to 100 μm. It is particularly preferable that both the D50 value and the D90 value lie in the range from 0.1 to 100 μm and, in particular, in the range from 1 to 40 μm.
[0013] As emulsões podem estar presentes como emulsões O/A ou A/O ou como emulsões múltiplas A/O/A ou O/A/O.[0013] The emulsions may be present as O/W or W/O emulsions or as multiple W/O/W or O/W/O emulsions.
[0014] Surpreendentemente, com as carnosinas foi descoberto um grupo de substâncias, que apresentam não apenas propriedades de substâncias ativas em parte conhecidas e em parte até agora não conhecidas em conexão com a proteção da pele contra danos induzidos pela luz e meio ambiente, mas também ainda são capazes, de manter as emulsões à base de fatores de proteção solar UV-A e/ou UV-B estáveis ao armazenamento também a temperaturas elevadas e durante espaços de tempo mais longos. Com isso, as carnosinas preenchem perfeitamente o perfil de requisitos descrito no início, em que essas conferem às formulações um efeito de ação e, ao mesmo tempo, ainda um objetivo funcional, a saber, atuam como estabilizador.[0014] Surprisingly, with carnosines a group of substances was discovered, which not only have properties of active substances partly known and partly not yet known in connection with the protection of the skin against damage induced by light and the environment, but they are also still capable of keeping emulsions based on UV-A and/or UV-B sun protection factors stable for storage also at elevated temperatures and for longer periods of time. With this, carnosines perfectly fulfill the profile of requirements described at the beginning, in which they give the formulations an action effect and, at the same time, still a functional objective, namely, they act as a stabilizer.
[0015] Por fatores de proteção solar UV (componente a) devem ser entendidas, por exemplo, substâncias orgânicas (filtros de proteção solar) presentes em forma líquida ou cristalina à temperatura am- biente, que são capazes, de absorver raios ultravioleta e liberar novamente a energia absorvida em forma de uma radiação de ondas longas, por exemplo, calor. Em geral, os fatores de proteção solar UV considerados cada por si só, são acessíveis em quantidades de 0,1 a 5 e preferivelmente 0,2 a 1% em peso. A quantidade total de fatores de proteção solar em uma preparação pode ser, contudo, significativamente maior e de acordo com o SPF (“sun protection factor”) pode perfazer até 25% em peso, preferivelmente cerca de 10 a cerca de 15% em peso.[0015] UV sun protection factors (component a) must be understood, for example, organic substances (sun protection filters) present in liquid or crystalline form at room temperature, which are capable of absorbing ultraviolet rays and releasing again the energy absorbed in the form of long-wave radiation, eg heat. In general, UV sun protection factors considered on their own, are available in amounts of 0.1 to 5 and preferably 0.2 to 1% by weight. The total amount of sun protection factors in a preparation can however be significantly higher and according to the SPF (“sun protection factor”) can amount to up to 25% by weight, preferably about 10 to about 15% by weight. .
[0016] Filtros UVB podem ser solúveis em óleo ou hidrossolúveis. Como substâncias solúveis em óleo são mencionadas, por exemplo: • 3-benzilideno cânfora ou 3-benzilidenonor cânfora e seus derivados, por exemplo, 3-(4-metilbenzilideno)cânfora; • derivados de 4-aminobenzóico, preferivelmente éster 2- etil-hexílico de ácido 4-(dimetilamino)benzóico, éster 2-octílico de ácido 4-(dimetilamino)benzóico e éster amílico de ácido 4-(dimetilamino)- benzóico; • éster do ácido cinâmico, preferivelmente éster 2-etil- hexílico de ácido 4-metoxicinâmico, éster propílico de ácido 4- metoxicinâmico, éster isoamílico de ácido 4-metoxicinâmico, éster 2- etil-hexílico de ácido 2-ciano-3,3-fenilcinâmico (octocrilene); • éster do ácido salicílico, preferivelmente éster 2-etil- hexílico de ácido salicílico, éster 4-isopropilbenzílico de ácido salicílico, éster homomentílico de ácido salicílico; • derivados da benzofenona, preferivelmente 2-hidróxi-4- metoxibenzofenona, 2-hidróxi-4-metóxi-4’-metilbenzofenona, 2,2’-di- hidróxi-4-metoxibenzofenona; • éster do ácido benzalmalônico, preferivelmente éster di-2- etil-hexílico de ácido 4-metoxibenzomalônico; • derivados de triazina, tais como, por exemplo, 2,4,6- trianilino-(p-carbo-2’-etil-1’-hexilóxi)-1,3,5-triazina e octil triazona ou dioctil butamido triazona (Uvasorb® HEB); • propan-1,3-dionas, tal como, por exemplo, 1-(4- terc.butilfenil)-3-(4’-metoxifenil)propan-1,3-diona; • derivados de cetotriciclo(5.2.1.0)decano.[0016] UVB filters can be oil soluble or water soluble. As oil-soluble substances, for example: • 3-benzylidene camphor or 3-benzylidenenor camphor and its derivatives, for example 3-(4-methylbenzylidene)camphor, are mentioned; • 4-aminobenzoic derivatives, preferably 4-(dimethylamino)benzoic acid 2-ethylhexyl ester, 4-(dimethylamino)benzoic acid 2-octyl ester and 4-(dimethylamino)-benzoic acid amyl ester; • cinnamic acid ester, preferably 4-methoxycinnamic acid 2-ethylhexyl ester, 4-methoxycinnamic acid propyl ester, 4-methoxycinnamic acid isoamyl ester, 2-cyano-3,3 2-ethylhexyl ester -phenylcinnamic (octocrylene); • salicylic acid ester, preferably salicylic acid 2-ethylhexyl ester, salicylic acid 4-isopropylbenzyl ester, salicylic acid homomenthyl ester; • benzophenone derivatives, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone; • benzalmalonic acid ester, preferably 4-methoxybenzomalonic acid di-2-ethylhexyl ester; • triazine derivatives, such as, for example, 2,4,6-trianilino-(p-carbo-2'-ethyl-1'-hexyloxy)-1,3,5-triazine and octyl triazone or dioctyl butamido triazone ( Uvasorb® HEB); • propan-1,3-diones, such as, for example, 1-(4-tert.butylphenyl)-3-(4'-methoxyphenyl)propan-1,3-dione; • ketotricyclo(5.2.1.0)decane derivatives.
[0017] Como substâncias hidrossolúveis são incluídos: • ácido 2-fenilbenzimidazol-5-sulfônico e sais dos mesmos de metais alcalinos, metais alcalino-terrosos, de amônio, alquilamônio, alcanolamônio e glucamônio; • ácido 1H-benzimidazol-4,6-dissulfônico, sal 2,2’-(1,4- fenileno)bis-dissódico (Neo Heliopan® AP) • derivados de ácido sulfônico de benzofenonas, preferivelmente ácido 2-hidróxi-4-metoxibenzofenon-5-sulfônico e sais dos mesmos; • derivados de ácido sulfônico da 3-benzilideno cânfora, tais como por exemplo, ácido 4-(2-oxo-3- bornilidenome- til)benzenossulfônico e ácido 2-metil-5-(2-oxo-3- bornilideno)sulfônico e sais dos mesmos.[0017] As water-soluble substances are included: • 2-phenylbenzimidazole-5-sulfonic acid and salts thereof of alkali metals, alkaline earth metals, ammonium, alkylammonium, alkanolammonium and glucammonium; • 1H-benzimidazole-4,6-disulfonic acid, 2,2'-(1,4-phenylene)bis-disodium salt (Neo Heliopan® AP) • sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4- methoxybenzophenon-5-sulfonic and salts thereof; • sulfonic acid derivatives of 3-benzylidene camphor, such as, for example, 4-(2-oxo-3-bornylidene-methyl)benzenesulfonic acid and 2-methyl-5-(2-oxo-3-bornylidene)sulfonic acid and salts of the same.
[0018] Como filtros UV-A típicos são incluídos, em particular, derivados do benzoilmetano, tais como, por exemplo, 1-(4’-terc.butilfenil)- 3-(4’-metoxifenil)propan-1,3-dona, 4-terc.-butil-4’-metóxi-dibenzoilmetano (Parsol® 1789), éster hexílico de ácido 2-(4- dietilamino-2-hidroxibenzoil)-benzóico (Uvinul® A Plus), 1-fenil-3-(4’- isopropilfenil)-propan-1,3-diona e compostos de enamina. Naturalmente, os filtros UV-A e UV-B também podem ser usados em misturas. Combinações particularmente favoráveis consistem nos derivados do benzoilmetano, por exemplo, 4-terc.-butil-4’-metoxidibenzoilmetano (Parsol® 1789) e éster 2-etil-hexílico de ácido 2-ciano-3,3- fenilcinâmico (octocrilene) em combinação com ésteres do ácido ci- nâmico, preferivelmente éster 2-etil-hexílico de ácido 4-metoxicinâmico e/ou éster propílico de ácido 4-metoxicinâmico e/ou éster isoamílico de ácido 4-metoxicinâmico. Vantajosamente, tais combinações são combinadas com filtros hidrossolúveis, tais como, por exemplo, ácido 2- fenilbenzimidazol-5-sulfônico e sais dos mesmos de metais alcalinos, alcalino-terrosos, amônio, alquilamônio, alcanolamônio e glucamônio.[0018] Typical UV-A filters include, in particular, benzoylmethane derivatives, such as, for example, 1-(4'-tert.butylphenyl)-3-(4'-methoxyphenyl)propan-1,3- dona, 4-tert.-butyl-4'-methoxy-dibenzoylmethane (Parsol® 1789), 2-(4-diethylamino-2-hydroxybenzoyl)-benzoic acid hexyl ester (Uvinul® A Plus), 1-phenyl-3 -(4'-isopropylphenyl)-propan-1,3-dione and enamine compounds. Of course, UV-A and UV-B filters can also be used in blends. Particularly favorable combinations are benzoylmethane derivatives, for example 4-tert-butyl-4'-methoxydibenzoylmethane (Parsol® 1789) and 2-cyano-3,3-phenylcinnamic acid 2-ethylhexyl ester (octocrylene) in combination with cinnamic acid esters, preferably 4-methoxycinnamic acid 2-ethylhexyl ester and/or 4-methoxycinnamic acid propyl ester and/or 4-methoxycinnamic acid isoamyl ester. Advantageously, such combinations are combined with water-soluble filters, such as, for example, 2-phenylbenzimidazole-5-sulfonic acid and alkali metal, alkaline earth, ammonium, alkylammonium, alkanolammonium and glucammonium salts thereof.
[0019] No caso das carnosinas, que compõem a fórmula (I) e que formam o componente (b), trata-se de compostos fundamentalmente conhecidos, que são acessíveis pelos processos usuais da química orgânica. Preferivelmente, trata-se neste caso, do grupo de substâncias, que é formado pela carnosina, L-carnosina, D-carnosina, D/L- carnosina, carnicina, carnicina*HCl, anserina, D-anserina, L-anserina e L-anserina*HNO3 e suas misturas.[0019] In the case of carnosines, which make up formula (I) and which form component (b), these are fundamentally known compounds, which are accessible by the usual processes of organic chemistry. Preferably, this is the group of substances which is formed by carnosine, L-carnosine, D-carnosine, D/L-carnosine, carnicine, carnicine*HCl, anserine, D-anserine, L-anserine and L -anserine*HNO3 and mixtures thereof.
[0020] Por sais dos compostos da fórmula (I) são entendidos, de acordo com a invenção, sais dos compostos da fórmula (I) com ácidos minerais e de modo particularmente preferido, sais da fórmula (II): [0020] By salts of the compounds of the formula (I) are understood, according to the invention, salts of the compounds of the formula (I) with mineral acids and particularly preferably salts of the formula (II):
[0021] na qual n representa 1, 2 ou 3 e A representa HCl ou HNO3 e R1 representa H ou CH3 e R2 representa H ou COOH.[0021] in which n represents 1, 2 or 3 and A represents HCl or HNO3 and R1 represents H or CH3 and R2 represents H or COOH.
[0022] O uso vantajoso de carnosinas no campo da profilaxia contra o envelhecimento da pele ou dano da pele induzido pela luz é sufi-cientemente conhecido a partir do estado da técnica.[0022] The advantageous use of carnosines in the field of prophylaxis against skin aging or light-induced skin damage is sufficiently known from the prior art.
[0023] Assim, a partir de uma pesquisa de Aruoma e colaborado res já do ano de 1989 sabe-se, por exemplo, que a carnosina é capaz de interceptar ROS (“reactive oxygen species”) [Biochem. J. 264(3), página 863-869 (1989)]. De acordo com um relato de Babizhayev e colaboradores, a carnosina pode interceptar, além disso, aldeídos alfa- beta-insaturados, que são libertados na peroxidação de ácidos graxos da membrana celular no estresse oxidativo [Membran & Cell Biol. 12(1), página 89-99 (1998)].[0023] Thus, from research carried out by Aruoma and collaborators in 1989, it is known, for example, that carnosine is capable of intercepting ROS (“reactive oxygen species”) [Biochem. J. 264(3), page 863-869 (1989)]. According to a report by Babizhayev et al., carnosine can additionally intercept alpha-beta-unsaturated aldehydes, which are released in the peroxidation of cell membrane fatty acids in oxidative stress [Membran & Cell Biol. 12(1), page 89-99 (1998)].
[0024] O documento EP 1310238 A2 (BASF) publica preparações cosméticas ou dermatológicas de protetores solares, que contêm pelo menos um componente cristalino líquido colestérico que reflete na faixa de comprimento de onda infravermelho de 750 nm até 2500 nm, pelo menos uma substância de filtro que protege contra a faixa de radiação ultravioleta de 280 nm até 449 nm e pelo menos um veículo cosmeticamente aceitável e seu uso. Além disso, podem ser acrescentados outros antioxidantes, tais como, por exemplo, carnosina.[0024] The document EP 1310238 A2 (BASF) publishes cosmetic or dermatological preparations of sunscreens, which contain at least one cholesteric liquid crystalline component that reflects in the infrared wavelength range from 750 nm to 2500 nm, at least one substance of filter that protects against the ultraviolet radiation range from 280 nm to 449 nm and at least one cosmetically acceptable carrier and its use. In addition, other antioxidants may be added, such as, for example, carnosine.
[0025] O documento EP 1388339 A1 (VISA) publica o uso de car- nosina para o controle do processo de envelhecimento, em que a formação de rugas da pele é invertida, prevenida e reduzida. A carnosina é designada como substância ativa antirrugas, que protege, entre outros, também contra a glicosilação e inflamações crônicas.[0025] EP 1388339 A1 (VISA) publishes the use of carnosine for the control of the aging process, whereby the formation of skin wrinkles is reversed, prevented and reduced. Carnosine is designated as an anti-wrinkle active substance, which protects, among others, also against glycosylation and chronic inflammation.
[0026] O objetivo do documento EP 2181697 A2 (SHISEIDO) são protetores solares em forma de O/A, que se destacam por um coquetel especial de emulsificantes e filtros de proteção solar. A tabela 3-3 publica duas composições (exemplos 22 e 23), que contêm a combinação de carnosina com filtros UV.[0026] The purpose of document EP 2181697 A2 (SHISEIDO) is sunscreens in the form of O/W, which are distinguished by a special cocktail of emulsifiers and sunscreen filters. Table 3-3 publishes two compositions (Examples 22 and 23), which contain the combination of carnosine with UV filters.
[0027] Além disso, a partir do documento EP 1591105 A1 (STA- DA) são conhecidas preparações cosméticas e farmacêutica, que contêm um antioxidante, que protegem a pele contra radiação infravermelha. Entre os inúmeros antioxidantes possíveis são mencionados também a carnosina e arnesina. Além disso, as composições a serem aplicadas topicamente compreendem um ou mais filtros UV inorgâni- cos e/ou orgânicos. Este relatório não contém uma publicação concreta para misturas de carnosinas e filtros UV.[0027] Furthermore, from EP 1591105 A1 (STADA) cosmetic and pharmaceutical preparations are known, which contain an antioxidant, which protect the skin against infrared radiation. Among the numerous possible antioxidants, carnosine and arnesine are also mentioned. Furthermore, the compositions to be applied topically comprise one or more inorganic and/or organic UV filters. This report does not contain a concrete publication for blends of carnosines and UV filters.
[0028] O documento EP 2545898 A1 (COTY) publica preparações, que protegem a pele contra danos devido aos raios infravermelhos e, neste caso, contêm extratos de plantas, vitaminas, rubina em pó, mica e dióxido de titânio. No parágrafo [0026] menciona-se também a car- nosina como outra substância auxiliar adequada, contudo como captu- rador de radicais. Este relatório também não contém uma publicação concreta para misturas de carnosinas e filtros UV.[0028] EP 2545898 A1 (COTY) publishes preparations, which protect the skin from damage due to infrared rays and, in this case, contain plant extracts, vitamins, rubin powder, mica and titanium dioxide. In paragraph [0026] carnosine is also mentioned as another suitable auxiliary substance, however as a radical scavenger. This report also does not contain a concrete publication for blends of carnosines and UV filters.
[0029] O pedido de patente internacional WO 1990 006102 A1 (PEPTIDE TECHNOLOGY) refere-se, do mesmo modo, à propriedade antioxidativa de compostos de carnosina. É publicado principalmente, que os compostos encontrados reduzem ou previnem as reticulações de colágeno na pele e/ou o dano das células cutâneas de DNA, em particular, provocado pelo envelhecimento ou radiação UV. A aplicação ocorre topicamente ou por meio de injeção. Uma referência à mistura com filtros UV não é encontrada no relatório.[0029] International patent application WO 1990 006102 A1 (PEPTIDE TECHNOLOGY) likewise relates to the antioxidative property of carnosine compounds. It is mainly reported that the compounds found reduce or prevent cross-linking of collagen in the skin and/or damage to skin DNA cells, in particular, caused by aging or UV radiation. Application occurs topically or by injection. A reference to mixing with UV filters is not found in the report.
[0030] O documento WO 2010 124817 A2 (KPSS) refere-se a agentes de condicionamento à base, entre outros, de dipeptídeos, tais como, por exemplo, carnosina, para os cabelos. Nos exemplos de concretização encontra-se uma publicação para a combinação de car- nosina com um filtro UV, a saber, benzofenona-3 nos exemplos 4, 8, 9 e 16, em que a relação de peso entre carnosina e benzofenona-3 está na faixa de 1:03 até 1:2.[0030] WO 2010 124817 A2 (KPSS) refers to conditioning agents based on, among others, dipeptides, such as, for example, carnosine, for hair. In the embodiment examples there is a publication for the combination of carnosine with a UV filter, namely benzophenone-3 in examples 4, 8, 9 and 16, wherein the weight ratio between carnosine and benzophenone-3 is in the range of 1:03 to 1:2.
[0031] Além disso, é feita referência ao pedido de patente interna cional WO 2014 128228 A2 (SYMRISE), que mostra a aptidão dessas substâncias para proteger contra radiação infravermelha com base na inibição da expressão MMP. De forma concreta, são publicadas aqui misturas de peso igual de carnosina com Uvinul A e octocrileno.[0031] Furthermore, reference is made to the international patent application WO 2014 128228 A2 (SYMRISE), which shows the ability of these substances to protect against infrared radiation based on the inhibition of MMP expression. Specifically, equal weight mixtures of carnosine with Uvinul A and octocrylene are published here.
[0032] O objetivo do documento US 2006/216251 A1 (TRACIE MARTIN) são composições tópicas, contendo carnosina, carnitina e um ácido lipônico, para o tratamento e proteção da pele, em particular, com respeito à indicação de envelhecimento da pele em relação ao envelhecimento cronológico (chrono-ageing) ou fotoenvelhecimento (foto-ageing), que é voltado às rugas, enfraquecimento da pele e perda da elasticidade. O tratamento voltado à hiperpigmentação é publicado do mesmo modo. No relatório é feita referência, do mesmo modo, à influência de carnosinas sobre a inibição MMP-1. Os exemplos 1 a 8 publicam uma quantidade de uso de carnosina na faixa de 1% em peso e 2% em peso.[0032] The purpose of document US 2006/216251 A1 (TRACIE MARTIN) is topical compositions, containing carnosine, carnitine and a liponic acid, for the treatment and protection of the skin, in particular, with respect to the indication of skin aging in relation to to chronological aging (chrono-ageing) or photo-aging (photo-aging), which is aimed at wrinkles, skin weakening and loss of elasticity. Treatment aimed at hyperpigmentation is published in the same way. Reference is also made in the report to the influence of carnosines on MMP-1 inhibition. Examples 1 to 8 publish a use amount of carnosine in the range of 1% by weight and 2% by weight.
[0033] De acordo com o resumo em inglês do documento KR 2004 0074795 A (A E KYUNG), 0,1 a 2% em peso, de carnosina em composições cosméticas apresentam um efeito antioxidativo sobre a pele e aumentam a síntese do colágeno. Como exemplo é indicada uma formulação contendo 0,1% em peso de carcinina (carnosina), 0,5% em peso, de ácido salicílico, 5,0% em peso, de 1,3-butilenoglicol, 1,3% em peso, de monolaurato de polietilenossorbitano, 0,7% em peso, de éter láurico de polietileno, 15% em peso, de etanol, 0,2% de aromatizantes, conservantes e água.[0033] According to the English abstract of document KR 2004 0074795 A (A E KYUNG), 0.1 to 2% by weight of carnosine in cosmetic compositions has an antioxidant effect on the skin and increases collagen synthesis. An example is a formulation containing 0.1% by weight of carcinine (carnosine), 0.5% by weight of salicylic acid, 5.0% by weight of 1,3-butylene glycol, 1.3% by weight , polyethylene sorbitan monolaurate, 0.7% by weight, polyethylene lauric ether, 15% by weight, ethanol, 0.2% flavorings, preservatives and water.
[0034] Contudo, a requerente verificou, além disso, que as carno- sinas aumentam, em particular, a atividade da produção de G6PDH e reage à apoptose. O uso das substâncias como medicamentos ou produtos de higiene protetores e reconstituintes é possível, em princípio, para todas as preparações, que são usadas para a prevenção contra danos ou em danos da pele e, com isso, no cuidado da pele e profilaxia. Um outro uso nesse campo é a aplicação na pele sensível, danificada devido à alergia ou outras origens. O dano da pele, neste caso, pode ter as mais variadas origens.[0034] However, the Applicant has further found that carnosines in particular increase the activity of G6PDH production and react to apoptosis. The use of substances as protective and restorative medicines or hygiene products is possible, in principle, for all preparations, which are used for the prevention of damage or damage to the skin and, therefore, in skin care and prophylaxis. Another use in this field is the application on sensitive skin, damaged due to allergy or other origins. The skin damage, in this case, can have the most varied origins.
[0035] A quantidade de aplicação usual das carnosinas perfaz, com base na emulsão, tipicamente em cerca de 0,001 a cerca de 2,5% em peso, preferivelmente cerca de 0,005 a 2% em peso e, em particular, cerca de 0,01 a cerca de 1,5% em peso.[0035] The usual application amount of carnosines amounts, based on the emulsion, typically to about 0.001 to about 2.5% by weight, preferably about 0.005 to 2% by weight, and in particular about 0.005 to about 2.5% by weight. 01 to about 1.5% by weight.
[0036] Como emulsificantes para as emulsões são incluídos, por exemplo, os agentes tensoativos não ionogênicos a partir de pelo menos um dos seguintes grupos: • produtos de adição de 2 a 30 mol de óxido de etileno e/ou 0 a 5 mol de óxido de propileno com álcoois graxos lineares com 8 a 22 átomos de carbono, com ácidos graxos com 12 a 22 átomos de carbono, com alquilfenóis com 8 a 15 átomos de carbono no grupo alquila e alquilaminas com 8 a 22 átomos de carbono no radical alquila; • oligoglicosídeos de alquila e/ou alquenila com 8 a 22 átomos de carbono no radical alqu(en)ila e seus análogos etoxilados; • produtos de adição de 1 a 15 mol de óxido de etileno com óleo de rícino e/ou óleo de rícino solidificado; • produtos de adição de 15 a 60 mol de óxido de etileno com óleo de rícino e/ou óleo de rícino solidificado; • ésteres parciais de glicerina e/ou sorbitano com ácidos graxos ramificados insaturados, lineares ou saturados com 12 a 22 átomos de carbono e/ou ácidos hidroxicarboxílicos com 3 a 18 átomos de carbono e seus adutos com 1 a 30 mol de óxido de etileno; • ésteres parciais de poliglicerina (grau de condensação próprio médio 2 a 8), polietilenoglicol (peso molecular 400 a 5000), tri- metilolpropano, pentaeritritol, álcoois de açúcares (por exemplo, sorbitol), alquilglicosídeos (por exemplo, glicosídeo de metila, glicosídeo de butila, glicosídeo de laurila) e poliglicosídeos (por exemplo, celulose) com ácidos graxos lineares ou ramificados, saturados e/ou insaturados com 12 a 22 átomos de carbono e/ou ácidos hidroxicarboxílicos com 3 a 18 átomos de carbono e seus adutos com 1 a 30 mol de óxido de etileno; • ésteres mistos de pentaeritritol, ácidos graxos, ácido cítrico e álcool graxo e/ou ésteres mistos de ácidos graxos com 6 a 22 átomos de carbono, metilglicose e polióis, preferivelmente glicerina ou poliglicerina. • Fosfatos de mono-, di- e trialquila e fosfatos de mono-, di- e/ou tri-PEG-alquila e sais dos mesmos; • álcoois de cera de lã; • copolímeros de polissiloxano-polialquila-poliéter ou derivados correspondentes; • copolímeros em bloco, por exemplo, dipoli- hidroxiestearatos de polietilenoglicol-30; • emulsificantes de polímeros, por exemplo, tipos Pemulen (TR-1 TR-2) de Goodrich ou Cosmedia® SP da Cognis; • polialquilenoglicóis e • carbonato de glicerina.[0036] As emulsifiers for emulsions, for example, non-ionogenic surfactants from at least one of the following groups are included: • addition products of 2 to 30 mol of ethylene oxide and/or 0 to 5 mol of propylene oxide with linear fatty alcohols of 8 to 22 carbon atoms, with fatty acids of 12 to 22 carbon atoms, with alkylphenols of 8 to 15 carbon atoms in the alkyl group, and alkylamines with 8 to 22 carbon atoms in the alkyl radical ; • alkyl and/or alkenyl oligoglycosides with 8 to 22 carbon atoms in the alk(en)yl radical and their ethoxylated analogues; • addition products of 1 to 15 mol of ethylene oxide with castor oil and/or solidified castor oil; • addition products of 15 to 60 mol of ethylene oxide with castor oil and/or solidified castor oil; • partial esters of glycerin and/or sorbitan with unsaturated, linear or saturated branched fatty acids with 12 to 22 carbon atoms and/or hydroxycarboxylic acids with 3 to 18 carbon atoms and their adducts with 1 to 30 mol of ethylene oxide; • partial esters of polyglycerin (average degree of condensation 2 to 8), polyethylene glycol (molecular weight 400 to 5000), trimethylolpropane, pentaerythritol, sugar alcohols (eg sorbitol), alkyl glycosides (eg methyl glycoside, butyl glycoside, lauryl glycoside) and polyglycosides (e.g. cellulose) with linear or branched, saturated and/or unsaturated fatty acids of 12 to 22 carbon atoms and/or hydroxycarboxylic acids of 3 to 18 carbon atoms and their adducts with 1 to 30 mol of ethylene oxide; • mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohol and/or mixed esters of fatty acids with 6 to 22 carbon atoms, methyl glucose and polyols, preferably glycerin or polyglycerin. • Mono-, di- and trialkyl phosphates and mono-, di- and/or tri-PEG-alkyl phosphates and salts thereof; • wool wax alcohols; • polysiloxane-polyalkyl-polyether copolymers or corresponding derivatives; • block copolymers, for example polyethylene glycol-30 dipolyhydroxystearates; • polymer emulsifiers, eg Pemulen types (TR-1 TR-2) from Goodrich or Cosmedia® SP from Cognis; • polyalkylene glycols and • glycerin carbonate.
[0037] A seguir, emulsificantes particularmente adequados são esclarecidos em detalhes:[0037] The following particularly suitable emulsifiers are clarified in detail:
[0038] Alcoxilatos: Os produtos de adição de óxido de etileno e/ou de óxido de propileno com álcoois graxos, ácidos graxos, alquil- fenóis ou com óleo de rícino representam produtos conhecidos, à venda no mercado. Neste caso, trata-se de misturas homólogas, cujo grau de alcoxilação médio corresponde à relação das quantidades de substâncias de óxido de etileno e/ou óxido de propileno e substrato, com os quais é realizada a reação de adição. Mono- e diésteres de ácido C12/18-graxo de produtos de adição de óxido de etileno com glicerina são conhecidos como hidratantes para preparações cosméticas.[0038] Alkoxylates: The products of ethylene oxide and/or propylene oxide additions with fatty alcohols, fatty acids, alkyl phenols or with castor oil represent known products for sale in the market. In this case, they are homologous mixtures, whose average degree of alkoxylation corresponds to the ratio of the amounts of ethylene oxide and/or propylene oxide substances and substrate, with which the addition reaction is carried out. C12/18-fatty acid mono- and diesters of ethylene oxide addition products with glycerin are known as moisturizers for cosmetic preparations.
[0039] Oligoglicosídeo de alquila e/ou alquenila. Oligoglicosí-deos de alquila e/ou alquenila, sua produção e seu uso são conhecidos a partir do estado da técnica. Sua produção ocorre, em particular, através da reação de glicose ou oligossacarídeos com álcoois primá- rios com 8 a 18 átomos de carbono. Com respeito ao radical glicosídeo vale, que tanto monoglicosídeos, nos quais um radical de açúcar cíclico está ligado glicosidicamente ao álcool graxo, como também glicosí- deos oligoméricos com um grau de oligomerização até preferivelmente cerca de 8, são adequados. O grau de oligomerização, neste caso, é um valor estatístico médio, que tem por base uma distribuição de homólogos para tais produtos técnicos.[0039] Alkyl and/or alkenyl oligoglycoside. Alkyl and/or alkenyl oligoglycosides, their production and their use are known from the state of the art. Its production occurs, in particular, through the reaction of glucose or oligosaccharides with primary alcohols with 8 to 18 carbon atoms. With respect to the glycoside moiety, it is noted that both monoglycosides, in which a cyclic sugar moiety is glycosidicly linked to the fatty alcohol, and also oligomeric glycosides with a degree of oligomerization up to preferably about 8, are suitable. The degree of oligomerization in this case is an average statistical value, which is based on a distribution of homologs for such technical products.
[0040] Glicerídeos parciais. Exemplos típicos para glicerídeos parciais adequados são o monoglicerídeo de ácido hidroxiesteárico, diglicerídeo de ácido hidroxiesteárico, monoglicerídeo de ácido isoes- teárico, diglicerídeo de ácido isoesteárico, monoglicerídeo de ácido oleico, diglicerídeo de ácido oleico, monoglicerídeo de ácido ricinólico, diglicerídeo de ácido ricinólico, monoglicerídeo de ácido linólico, digli- cerídeo de ácido linólico, monoglicerídeo de ácido linolênico, diglicerí- deo de ácido linolênico, monoglicerídeo de ácido erúcico, diglicerideo de ácido erúcico, monoglicerídeo de ácido tartárico, diglicerídeo de ácido tartárico, monoglicerídeo de ácido cítrico, diglicerídeo de ácido cítrico, monoglicerídeo de ácido málico, diglicerídeo de ácido málico e suas misturas técnicas que, subordinadas do processo de produção, ainda podem conter pequenas quantidades de triglicerídeo. Do mesmo modo, são adequados os produtos de adição de 1 a 30, preferivelmente 5 a 10 mol de óxido de etileno com os glicerídeos parciais mencionados.[0040] Partial glycerides. Typical examples for suitable partial glycerides are hydroxystearic acid monoglyceride, hydroxystearic acid diglyceride, isostearic acid monoglyceride, isostearic acid diglyceride, oleic acid monoglyceride, oleic acid diglyceride, ricinolic acid monoglyceride, ricinolic acid diglyceride, linolenic acid monoglyceride, linolic acid diglyceride, linolenic acid monoglyceride, linolenic acid diglyceride, erucic acid monoglyceride, erucic acid diglyceride, tartaric acid monoglyceride, tartaric acid diglyceride, citric acid monoglyceride, diglyceride of citric acid, monoglyceride of malic acid, diglyceride of malic acid and their technical mixtures which, subordinate to the production process, may still contain small amounts of triglyceride. Likewise, addition products of 1 to 30, preferably 5 to 10 mol of ethylene oxide with the mentioned partial glycerides are suitable.
[0041] Ésteres de sorbitano. Como ésteres de sorbitano são incluídos o monoisoestearato de sorbitano, sesquiisoestearato de sorbi- tano, di-isoestearato de sorbitano, triisoestearato de sorbitano, monoo- leato de sorbitano, sesquioleato de sorbitano, dioleato de sorbitano, trioleato de sorbitano, monoerucato de sorbitano, sesquierucato de sorbitano, dierucato de sorbitano, trierucato de sorbitano, monoricino- leato de sorbitano, sesquiricinoleato de sorbitano, diricinoleato de sor- bitano, triricinoleato de sorbitano, monohidroxiestearato de sorbitano, sesquihidroxiestearato de sorbitano, di-hidroxiestearato de sorbitano, tri-hidroxiestearato de sorbitano, monotartrato de sorbitano, sesquitar- trato de sorbitano, ditartrato de sorbitano, tritartrato de sorbitano, monocitrato de sorbitano, sesquicitrato de sorbitano, dicitrato de sorbita- no, tricitrato de sorbitano, monomaleato de sorbitano, sesquimaleato de sorbitano, dimaleato de sorbitano, trimaleato de sorbitano e suas misturas técnicas. Do mesmo modo, são adequados os produtos de adição de 1 a 30, preferivelmente 5 a 10 mol de óxido de etileno com os ésteres de sorbitano mencionados.[0041] Sorbitan esters. As sorbitan esters are included sorbitan monoisostearate, sorbitan sesquiostearate, sorbitan diisostearate, sorbitan triisostearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan dioleate, sorbitan trioleate, sorbitan monoerucate, sesquierucate Sorbitan Dierucate, Sorbitan Dierucate, Sorbitan Trierucate, Sorbitan Monoricinoleate, Sorbitan Sesquirinoleate, Sorbitan Diricinoleate, Sorbitan Triricinoleate, Sorbitan Monohydroxystearate, Sorbitan Sesquihydroxystearate, Sorbitan Dihydroxystearate, Sorbitan Trihydroxystearate , sorbitan monotartrate, sorbitan sesquitartrate, sorbitan ditartrate, sorbitan tritartrate, sorbitan monocitrate, sorbitan sesquicitrate, sorbitan dicitrate, sorbitan tricitrate, sorbitan monomaleate, sorbitan sesquimaleate, sorbitan dimaleate, trimaleate of sorbitan and its technical mixtures. Likewise, addition products of 1 to 30, preferably 5 to 10 mol of ethylene oxide with the mentioned sorbitan esters are suitable.
[0042] Ésteres poliglicéricos. Exemplos típicos de ésteres poli- glicéricos adequados são poliglicerol-2 dipoli-hidroxiestearatos (Dehymuls® PGPH), poliglicerin-3 di-isoestearato (Lameform® TGI), poliglicerol-4 isoestearato (Isolan® GI 34), poliglicerol-3 oleato, di- isoestearoil poliglicerol-3 di-isoestearato (Isolan® PDI), diestearato de poliglicerol-3 metilglicose (Tego Care® 450), poligicerol-3 cera de abelhas (Cera Bellina®), polilglicerol-4 caprato (poliglicerol caprato T2010/90), éter poliglicerol-3 cetílico (Chimexane® NL), poliglicerol-3 diestearato (Cremophor® GS 32) e poliglicerol polirinoleato (Admul® WOL 1403), isoestearato de poliglicerol dimerato e suas misturas. Exemplos de outros ésteres de poliol adequados são os mono-, di- e triésteres de trimetilolpropano reagidos com 1 a 30 mol de óxido de etileno ou pentaeritritol com ácido láurico, ácido graxo de coco, ácido graxo esteárico, ácido palmítico, ácido esteárico, ácido oleico, ácido behênico e similares.[0042] Polyglyceric esters. Typical examples of suitable polyglyceric esters are polyglycerol-2-dipolyhydroxystearate (Dehymuls® PGPH), polyglycerin-3-di-isostearate (Lameform® TGI), polyglycerol-4-isostearate (Isolan® GI 34), polyglycerol-3 oleate, di - isostearoyl polyglycerol-3 di-isostearate (Isolan® PDI), polyglycerol-3 methylglucose distearate (Tego Care® 450), polyglycerol-3 beeswax (Cera Bellina®), polyglycerol-4 caprate (polyglycerol caprate T2010/90) , polyglycerol-3 cetyl ether (Chimexane® NL), polyglycerol-3 distearate (Cremophor® GS 32) and polyglycerol polyrinoleate (Admul® WOL 1403), polyglycerol isostearate dimerate and mixtures thereof. Examples of other suitable polyol esters are the mono-, di- and triesters of trimethylolpropane reacted with 1 to 30 mol of ethylene oxide or pentaerythritol with lauric acid, coconut fatty acid, stearic fatty acid, palmitic acid, stearic acid, oleic acid, behenic acid and the like.
[0043] Emulsificantes aniônicos. Emulsificantes aniônicos típicos são ácidos graxos alifáticos com 12 a 22 átomos de carbono, tais como, por exemplo, ácido palmítico, ácido esteárico ou ácido behênico e ácidos dicarboxílicos com 12 a 22 átomos de carbono, tais como, por exemplo, ácido azelaico ou ácido sebácico.[0043] Anionic emulsifiers. Typical anionic emulsifiers are aliphatic fatty acids of 12 to 22 carbon atoms, such as, for example, palmitic acid, stearic acid or behenic acid, and dicarboxylic acids of 12 to 22 carbon atoms, such as, for example, azelaic acid or sebacic.
[0044] Emulsificantes anfóteros e catiônicos. Além disso, como emulsificantes podem ser usados os agentes tensoativos bipolares, Como agentes tensoativos bipolares são designados aqueles compostos tensoativos, que portam na molécula pelo menos um grupo amônio quaternário e pelo menos um grupo carboxilato e um grupo sulfonato. Agentes tensoativos bipolares particularmente adequados são as chamadas betaínas, tais como os glicinatos de N-alquil-N,N- dimetilamônio, por exemplo, o glicinato de coco-alquildimetilamônio, glicinatos de N-acilaminopropil-N,N-dimetilamônio, por exemplo, o gli- cinato de coco-acilaminopropildimetilamônio e 2-alquil-3-carboxilmetil- 3-hidroxietilimidazolina com 8 a 18 átomos de carbono cada no grupo alquila ou acila e o glicinato de coco-acilaminoetil- hidroxietilcarboximetila. Particularmente preferido é o derivado de ami- da de ácido graxo conhecido pela designação CTFA coo cocamido- propil betaina. Emulsificantes adequados, do mesmo modo, são os agentes tensoativos anfolíticos. Por agentes tensoativos anfolíticos são entendidos aqueles compostos tensoativos, que além de um grupo C8/18-alquila ou acila, contém na molécula pelo menos um grupo amino livre e pelo menos um grupo COOH ou SO3H e são capazes de formar sais internos. Exemplos de agentes tensoativos anfolíticos adequados são N-alquilglicinas, ácidos N-alquilpropiônicos, ácidos N- alquilaminobutíricos, ácidos N-alquiliminodipropiônicos, N-hidroxietil-N- alquilamidopropilglicinas, N-alquiltaurinas, N-alquilsarcosinas, ácidos 2-alquilaminopropiônicos e ácidos alquilaminoacéticos com cerca de 8 a 18 átomos de carbono cada no grupo alquila. Agentes tensoativos anfolíticos particularmente preferidos são o N-coco- alquilaminopropionato, o coco-acilaminoetilaminopropionato e a C12/18- acilsarcosina. Finalmente, os agentes tensoativos catiônicos também são incluídos como emulsificantes, sendo que aqueles do tipo dos es- terquats, preferivelmente sais de éster trietanolamínico de ácido digra-xo são particularmente preferidos.[0044] Amphoteric and cationic emulsifiers. In addition, bipolar surfactants can be used as emulsifiers. Bipolar surfactants are designated as surfactant compounds which bear in the molecule at least one quaternary ammonium group and at least one carboxylate group and one sulfonate group. Particularly suitable bipolar surfactants are so-called betaines, such as N-alkyl-N,N-dimethylammonium glycinates, e.g. coco-alkyldimethylammonium glycinate, N-acylaminopropyl-N,N-dimethylammonium glycinates, e.g. coco-acylaminopropyldimethylammonium glycinate and 2-alkyl-3-carboxylmethyl-3-hydroxyethylimidazoline with 8 to 18 carbon atoms each in the alkyl or acyl group; and coco-acylaminoethylhydroxyethylcarboxymethyl glycinate. Particularly preferred is the fatty acid amide derivative known by the designation CTFA such as cocamido-propyl betaine. Suitable emulsifiers, likewise, are ampholytic surfactants. Ampholytic surface-active agents are understood to be those surface-active compounds which, in addition to a C8/18-alkyl or acyl group, contain in the molecule at least one free amino group and at least one COOH or SO3H group and are capable of forming internal salts. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids with about 8 to 18 carbon atoms each in the alkyl group. Particularly preferred ampholytic surfactants are N-coco-alkylaminopropionate, coco-acylaminoethylaminopropionate and C12/18-acylsarcosine. Finally, cationic surfactants are also included as emulsifiers, with those of the esterquat type, preferably digra-xo acid triethanolamine ester salts being particularly preferred.
[0045] Em muitos casos, foi provado ser vantajoso usar combina ções de diferentes emulsificantes, a saber, misturas binárias (por exemplo, poliglicosídeo de alquila/etoxilato de álcool graxo) ou misturas ternárias (por exemplo, poliglicosídeo de alquila/benzenossulfonato de alquila/esterquat ou monoglicerídeo/etoxilato de álcool graxo/álcool graxo).[0045] In many cases, it has proved advantageous to use combinations of different emulsifiers, namely binary mixtures (e.g. alkyl polyglycoside/fatty alcohol ethoxylate) or ternary mixtures (e.g. alkyl polyglycoside/alkyl benzenesulfonate). /esterquat or monoglyceride/fatty alcohol ethoxylate/fatty alcohol).
[0046] A quantidade de aplicação dos emulsificantes pode situar-se entre cerca de 1 e cerca de 30% em peso. São preferidas faixas de cerca de 2 a 20 e, em particular, cerca de 5 a 10% em peso. Combinações correspondentemente preferidas são retiradas dos exemplos de concretização.[0046] The amount of application of the emulsifiers can be between about 1 and about 30% by weight. Ranges of about 2 to 20 and in particular about 5 to 10% by weight are preferred. Correspondingly preferred combinations are taken from the embodiment examples.
[0047] Tanto as emulsões podem conter veículos ou solvents como componente opcional (d1), que são selecionados a partir do grupo formado por água, álcoois, ésteres, butilenoglicol, dipropilenoglicol, etanol, etoxidiglicol, acetato de etila, glicerina, propanol, isopropanol, macrogóis, éter metílico de propilpropilenoglicol (2), éter metílico de propilpropilenoglicol (3), propilenocarbonato, propilenoglicol, trietileno- glicol, isoparafina, acetato de amila, benzoato de amila, acetato de benzila, acetato de butila, butilenoglicol, butil-lactato, benzoato de bu- to-octila, salicilato de buto-octila, C10-C13 alcanos, C14-C17 alcanos, C11-C15 cicloalcanos, butirato de caprilila, isoparafinas, diacetina, éter triacetino dicaprilíco, maleato de dicaprilila e suas misturas.[0047] Both emulsions may contain vehicles or solvents as an optional component (d1), which are selected from the group formed by water, alcohols, esters, butylene glycol, dipropylene glycol, ethanol, ethoxydiglycol, ethyl acetate, glycerin, propanol, isopropanol , macrogols, propylene glycol methyl ether (2), propylene glycol methyl ether (3), propylene carbonate, propylene glycol, triethylene glycol, isoparaffin, amyl acetate, amyl benzoate, benzyl acetate, butyl acetate, butylene glycol, butyl lactate , buto-octyl benzoate, buto-octyl salicylate, C10-C13 alkanes, C14-C17 alkanes, C11-C15 cycloalkanes, caprylyl butyrate, isoparaffins, diacetin, dicaprylyl triacetin ether, dicaprylyl maleate and mixtures thereof.
[0048] A proporção dos veículos na emulsão pode perfazer até 50% em peso e geralmente está na faixa de cerca de 25% em peso e, em particular, cerca de 10 a cerca de 15% em peso.[0048] The proportion of the vehicles in the emulsion can be up to 50% by weight and is generally in the range of about 25% by weight, and in particular about 10 to about 15% by weight.
[0049] Além disso, as emulsões podem apresentar substâncias oleosas (componente d2). Para esse fim, são incluídos, por exemplo, álcoois de Guerbet à base de álcoois graxos com 6 a 18, preferivelmente 8 a 10 átomos de carbono, ésteres de ácidos C6-C22-graxos lineares com álcoois C6-C22-graxos lineares ou ramificados ou ésteres de ácidos C6-C13-carboxílicos ramificados com álcoois C6-C22-graxos lineares ou ramificados, tais como, por exemplo, miristato de miristila, palmitato de miristila, estearato de miristila, isoestearato de miristila, oleato de miristila, behenato de miristila, erucato de miristila, miristato de cetila, palmitato de cetila, estearato de cetila, isoestearato de cetila, oleato de cetila, behenato de cetila, erucato de cetila, miristato de es- tearila, palmitato de estearila, estearato de estearila, isoestearato de estearila, oleato de estearila, behanato de estearila, erucato de esteari- la, miristato de isoestearila, palmitato de isoestearila, estearato de isoestearila, isoestearato de isoestearila, oleato de isoestearila, behe- nato de isoestearila, oleato de isoestearila, miristato de oleila, palmita- to de oleila, estearato de oleila, isoestearato de oleila, oleato de oleila, behenato de oleila, erucato de oleila, miristato de behenila, palmitato de behenila, estearato de behenila, isoestearato de behenila, oleato de behenila, behenato de behenila, erucato de behenila, miristato de eru- cila, palmitato de erucila, estearato de erucila, isoestearato de erucila, oleato de erucila, behenato de erucila e erucato de erucila. Além disso, são adequados os ésteres de ácidos C6-C22-graxos lineares com álcoois ramificados, em particular, 2-etil-hexanol, ésteres de ácidos C18- C38-alquil-hidroxicarboxílicos com álcoois C6-C22-graxos lineares ou ramificados, em particular, malatos de diocila, ésteres de ácidos gra- xos lineares e/ou ramificados com álcoois polivalentes (tais como, por exemplo, propilenoglicol, dimerodiol ou trimerotriol) e/ou álcoois de Guerbet, triglicerídeos à base de ácidos C6-C10-graxos, misturas líquidas de mono-/di-/triglicerídeos à base de ácidos C6-C18-graxos, ésteres de álcoois C6-C22-graxos e/ou álcoois de Guerbet com ácidos carboxí- licos aromáticos, em particular, ácido benzóico, ésteres de ácidos C2- C12-dicarboxílicos com álcoois lineares ou ramificados com 1 a 22 átomos de carbono ou polióis com 2 a 10 átomos de carbono e 2 a 6 grupos hidroxila, óleos vegetais, álcoois primários ramificados, ciclo- hexanos substituídos, carbonatos de álcoois C6-C22-graxos lineares ou ramificados, tais como, por exemplo, carbonatos de dicaprilila (Cetiol® CC), carbonatos de Guerbet à base de álcoois graxos com 6 a 18, preferivelmente 8 a 10 átomos de carbono, ésteres do ácido benzóico com álcoois C6-C22 lineares e/ou ramificados (por exemplo, Finsolv® TN), éteres dialquílicos simétricos ou assimétricos, lineares ou ramificados com 6 a 22 átomos de carbono por grupo alquila, tais como, por exemplo, éter dicaprílico (Cetiol® OE), produtos de abertura de anel de ésteres de ácidos graxos epoxidados com polióis, óleos de silicone (ciclometicona, tipos de silício meticona e outros) e/ou hidrocarbonetos alifáticos ou naftênicos, tais como, por exemplo, esqualano, esqualeno ou dialquilciclo-hexanos.[0049] In addition, emulsions may contain oily substances (component d2). For this purpose, for example, Guerbet alcohols based on fatty alcohols with 6 to 18, preferably 8 to 10 carbon atoms, esters of linear C6-C22-fatty acids with linear or branched C6-C22-fatty alcohols are included. or esters of branched C6-C13-carboxylic acids with linear or branched C6-C22-fatty alcohols, such as, for example, myristyl myristate, myristyl palmitate, myristyl stearate, myristyl isostearate, myristyl oleate, myristyl behenate , myristyl erucate, cetyl myristate, cetyl palmitate, cetyl stearate, cetyl isostearate, cetyl oleate, cetyl behenate, cetyl erucate, stearyl myristate, stearyl palmitate, stearyl stearate, stearyl isostearate , stearyl oleate, stearyl behanate, stearyl erucate, isostearyl myristate, isostearyl palmitate, isostearyl stearate, isostearyl isostearate, isostearyl oleate, isostearyl behenate, isostearyl oleate, oleyl myristate, oleyl palmitate, oleyl stearate, oleyl isostearate, oleyl oleate, oleyl behenate, oleyl erucate, behenyl myristate, behenyl palmitate, behenyl stearate, behenyl isostearate, behenyl oleate, behenyl behenate, behenyl erucate, erucill myristate, erucill palmitate, erucill stearate, erucill isostearate, erucill oleate, erucill behenate and erucyl erucate. In addition, esters of linear C6-C22-fatty acids with branched alcohols, in particular 2-ethyl-hexanol, esters of C18-C38-alkyl-hydroxycarboxylic acids with linear or branched C6-C22-fatty alcohols, in in particular, diocyl malates, esters of linear and/or branched fatty acids with polyvalent alcohols (such as, for example, propylene glycol, dimerodiol or trimerotriol) and/or Guerbet alcohols, triglycerides based on C6-C10-fatty acids , liquid mixtures of mono-/di-/triglycerides based on C6-C18-fatty acids, esters of C6-C22-fatty alcohols and/or Guerbet alcohols with aromatic carboxylic acids, in particular benzoic acid, esters of C2-C12-dicarboxylic acids with linear or branched alcohols of 1 to 22 carbon atoms or polyols of 2 to 10 carbon atoms and 2 to 6 hydroxyl groups, vegetable oils, branched primary alcohols, substituted cyclohexanes, carbonates of C6 alcohols -C22-linear or branched fats, t such as, for example, dicaprylyl carbonates (Cetiol® CC), Guerbet carbonates based on fatty alcohols with 6 to 18, preferably 8 to 10 carbon atoms, benzoic acid esters with linear and/or branched C6-C22 alcohols (e.g. Finsolv® TN), symmetrical or asymmetrical, linear or branched dialkyl ethers with 6 to 22 carbon atoms per alkyl group, such as, for example, dicapryl ether (Cetiol® OE), ring-opening products of esters of fatty acids epoxidized with polyols, silicone oils (cyclomethicone, methicone silicon types and others) and/or aliphatic or naphthenic hydrocarbons, such as, for example, squalane, squalene or dialkylcyclohexanes.
[0050] A proporção das substâncias oleosas na emulsão pode perfazer até 50% em peso e situa-se geralmente na faixa de cerca de 5 a cerca de 25% em peso e, em particular, cerca de 10 a cerca de 15% em peso.[0050] The proportion of the oily substances in the emulsion can be up to 50% by weight and is generally in the range of about 5 to about 25% by weight and in particular about 10 to about 15% by weight .
[0051] As emulsões de acordo com a invenção podem apresentar outras substâncias auxiliares e aditivas típicas, tais como, por exemplo, agentes tensoativos suaves, ceras de brilho perolar, agentes que conferem consistência, espessantes, agentes de re-engorduramento, estabilizadores, polímeros, compostos de silicone, graxas, ceras, lecitinas, fosfolipídeos, fatores de proteção solar UV, umectantes, substâncias ativas biogênicas, antioxidantes, desodorantes, antitranspiran- tes, repelentes de insetos, autobronzeadores, inibidores da tirosina (agentes de despigmentação), hidrotrópicos, solubilizantes, conservantes, óleos de perfume, corantes e conter similares.[0051] The emulsions according to the invention may have other typical auxiliary substances and additives, such as, for example, mild surface-active agents, pearl luster waxes, consistency-giving agents, thickeners, re-greasing agents, stabilizers, polymers , silicone compounds, greases, waxes, lecithins, phospholipids, UV sun protection factors, humectants, biogenic active substances, antioxidants, deodorants, antiperspirants, insect repellents, self-tanning products, tyrosine inhibitors (depigmentation agents), hydrotropics, solubilizers, preservatives, perfume oils, dyes and the like.
[0052] Como substâncias tensoativas podem estar contidos agentes tensoativos aniônicos, não iônicos, catiônicos e/ou anfóteros ou bipolares; a descrição dessas substâncias se sobrepõe com aquela para os emulsificantes, visto que as duas dispõem de propriedades tensoativas.[0052] Anionic, nonionic, cationic and/or amphoteric or bipolar surfactants may be contained as surfactants; the description of these substances overlaps with that for emulsifiers, since both have surface-active properties.
[0053] Exemplos típicos de agentes tensoativos aniônicos são sabões, benzenossulfonatos de alquila, alcanossulfonatos, sulfonatos de olefina, sulfonatos de éter alquílico, sulfonatos de éter glicérico, sulfonatos de éster a-metílico, ácidos sulfograxos, sulfatos de alquila, sulfatos de éter alquílico, sulfatos de éter glicérico, sulfatos de éter de ácido graxo, sulfatos de éter misto de hidróxi, sulfatos de (éter) de monogli- cerídeos, sulfatos de (éter) de amida de ácido graxo, sulfossuccinatos de mono- e dialquila, sulfossuccinamatos de mono- e dialquila, sulfo- triglicerídeos, sabões de amida, ácidos étercarboxílicos e sais dos mesmos, isetionatos de ácido graxo, sarcosinatos de ácido graxo, tau- ridas de ácido graxo, N-acilaminoácidos, tais como, por exemplo, lacti- latos de acila, tartratos de acila, glutamatos de acila e aspartatos de acila, sulfatos de oligoglicosídeo de alquila, condensados de ácidos graxos de proteína (em particular, produtos vegetais à base de trigo) e fosfatos de (éter) alquílico. A menos que os agentes tensoativos aniô- nicos contenham cadeias de éter poliglicólico, esses podem apresentar uma distribuição de homólogos convencional, preferivelmente, contudo, uma estreita. Exemplos típicos de agentes tensoativos não iôni- cos são o éter poliglicólico de álcool graxo, éter alquilfenolpoliglicólico, éster poliglicólico de ácido graxo, éter poliglicólico de amida de ácido graxo, éter poliglicólico de amina graxa, triglicerídeos alcoxilados, éteres mistos ou formais mistos, oligoglicosídeos de alqu(en)ila opcionalmente parcialmente oxidados ou derivados de ácido glicurônico, N- alquilglucamidas de ácido graxo, hidrolisados de proteína (em particu- lar, produtos vegetais à base de trigo), ésteres de ácido poliol graxo, éster de açúcar, éster de sorbitano, polissorbatos e óxidos de amina. A menos que os agentes tensoativos contenham cadeias de éter poligli- cólico, esses podem apresentar uma distribuição de homólogos convencional, preferivelmente, contudo, uma estreita. Exemplos típicos de agentes tensoativos catiônicos são compostos de amônio quaternário, tais como, por exemplo, o cloreto de dimetildiestearilamônio e ester- quats, em particular, sais de éster de trialcanolamina de ácido graxo quaternário. Exemplos típicos de agentes tensoativos anfóteros ou bi- polares são alquilbetaínas, alquilamidobetaínas, aminopropionatos, aminoglicinatos, betaínas de imidazolínio e sulfobetaínas. No caso dos agentes tensoativos mencionados trata-se exclusivamente de compostos conhecidos. Exemplos típicos de agentes tensoativos suaves particularmente adequados, isto é, agentes tensoativos particularmente compatíveis com a pele são os sulfatos de éter poliglicólico de álcool graxo, sulfatos de monoglicerídeos, mono- e/ou dialquilsulfossuccina- tos, isetionatos de ácidos graxos, sarcosinatos de ácidos graxos, tauri- das de ácidos graxos, glutamatos de ácidos graxos, sulfonatos de α- olefina, ácidos étercarboxílicos, oligoglicosídeos de alquila, glucamidas de ácidos graxos, alquilamidobetaínas, anfoacetais e/ou condensados de ácidos graxos de proteína, os últimos preferivelmente à base de proteínas de trigo.[0053] Typical examples of anionic surfactants are soaps, alkyl benzenesulfonates, alkanesulfonates, olefin sulfonates, alkyl ether sulfonates, glyceric ether sulfonates, a-methyl ester sulfonates, sulfofatty acids, alkyl sulfates, alkyl ether sulfates , glyceric ether sulfates, fatty acid ether sulfates, hydroxy mixed ether sulfates, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, mono- and dialkyl sulfosuccinates, mono- and dialkyl, sulfo-triglycerides, amide soaps, ether carboxylic acids and salts thereof, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, N-acylamino acids such as, for example, lactylates of acyl, acyl tartrates, acyl glutamates and acyl aspartates, alkyl oligoglycoside sulfates, fatty acid condensates from protein (in particular, wheat-based plant products) and phosphate those of alkyl (ether). Unless the anionic surfactants contain polyglycolic ether chains, they may have a conventional homolog distribution, preferably, however, a narrow one. Typical examples of non-ionic surfactants are fatty alcohol polyglycolic ether, alkylphenol polyglycolic ether, fatty acid polyglycolic ester, fatty acid amide polyglycolic ether, fatty amine polyglycolic ether, alkoxylated triglycerides, mixed or mixed formal ethers, oligoglycosides of alkyl(en)yl optionally partially oxidized or derivatives of glucuronic acid, fatty acid N-alkyl glucamides, protein hydrolysates (in particular wheat-based plant products), polyol fatty acid esters, sugar ester, ester of sorbitan, polysorbates and amine oxides. Unless the surfactants contain polyglycol ether chains, they may have a conventional, preferably, however, a narrow homolog distribution. Typical examples of cationic surfactants are quaternary ammonium compounds, such as, for example, dimethyldistearyl ammonium chloride and esterquats, in particular, quaternary fatty acid trialkanolamine ester salts. Typical examples of amphoteric or bi-polar surfactants are alkylbetaines, alkylamidobetains, aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines. In the case of the surfactants mentioned, these are exclusively known compounds. Typical examples of particularly suitable mild surfactants, i.e. particularly skin-friendly surfactants, are fatty alcohol polyglycolic ether sulfates, monoglyceride sulfates, mono- and/or dialkyl sulfosuccinates, fatty acid isethionates, acid sarcosinates fatty acids, fatty acid taurides, fatty acid glutamates, α-olefin sulfonates, ether carboxylic acids, alkyl oligoglycosides, fatty acid glucamides, alkylamidobetaines, amphoacetals and/or protein fatty acid condensates, the latter preferably based on of wheat proteins.
[0054] Exemplos típicos de graxas são glicerídeos, isto é, produtos vegetais ou animais, sólidos ou líquidos, que consistem essencialmente em ésteres glicéricos misturados de ácidos graxos superiores, como ceras são incluídas, entre outras, ceras naturais, tais como, por exemplo, cera de candelila, cera de carnaúba, cera japonesa, cera de esparto, cera de cortiça, cera de guarum, cera de óleo de gérmen de arroz, cera de cana-de-açúcar, cera de ouricuri, cera montana, cera de abelhas, cera de goma-laca, espermacete, lanolina (cera de lã), gordura de rabadilha, ceresina, ozoquerita (cera mineral), petrolato, cera de parafina, microceras; ceras quimicamente modificadas (ceras sólidas), tais como, por exemplo, ceras de éster montana, ceras de sasol, ceras de jojoba hidrogenadas e ceras sintéticas, tais como, por exemplo, ceras de polialquileno e ceras de polietilenoglicol. Além das graxas, são incluídas como substâncias aditivas também as substâncias similares à graxa, tais como lecitinas e fosfolipídeos. Pela designação lecitinas, o especialista entende aqueles glicero-fosfolipídeos, que se formam a partir de ácidos graxos, glicerina, ácido fosfórico e colina através de esterificação. No mundo científico, as lecitinas, por conseguinte, também são frequentes como fosfatidilcolinas (PC). Como exemplos de lecitinas naturais sejam mencionadas as cefalinas, que também são designadas coo ácidos fosfatídicos e representam derivados de ácidos 1,2-diacil-sn-glicerin-3-fosfóricos. Por outro lado, entendem-se por fos- folipídeos usualmente os mono- e preferivelmente diésteres do ácido fosfórico com glicerina (fosfatos de glicerina), que são geralmente acrescentados às graxas. Além disso, também são incluídas esfingo- sinas ou esfingolipídeos.[0054] Typical examples of greases are glycerides, i.e. vegetable or animal products, solid or liquid, which consist essentially of mixed glyceric esters of higher fatty acids, as waxes are included, among others, natural waxes, such as, for example, , candelilla wax, carnauba wax, japanese wax, esparto wax, cork wax, guarum wax, rice germ oil wax, sugar cane wax, ouricuri wax, montane wax, beeswax , shellac wax, spermaceti, lanolin (wool wax), rump fat, ceresin, ozokerite (mineral wax), petrolatum, paraffin wax, microwaxes; chemically modified waxes (solid waxes), such as, for example, montane ester waxes, sasol waxes, hydrogenated jojoba waxes, and synthetic waxes, such as, for example, polyalkylene waxes and polyethylene glycol waxes. In addition to greases, substances similar to grease, such as lecithins and phospholipids, are also included as additives. By the designation lecithins, the expert understands those glycero-phospholipids, which are formed from fatty acids, glycerin, phosphoric acid and choline through esterification. In the scientific world, lecithins, therefore, are also frequent as phosphatidylcholines (PC). As examples of natural lecithins, mention should be made of cephalins, which are also called phosphatidic acids and represent derivatives of 1,2-diacyl-sn-glycerin-3-phosphoric acids. On the other hand, phospholipids are usually understood to mean the mono- and preferably diesters of phosphoric acid with glycerin (glycerin phosphates), which are generally added to greases. In addition, sphingosines or sphingolipids are also included.
[0055] Como ceras de brilho perolar são incluídos, por exemplo: éster alquilenoglicólico, especialmente diestearato de etilenoglicol; al- canolamidas de ácido graxo, especialmente dietanolamida de ácido graxo de coco; glicerídeos parciais, especialmente monoglicerídeo de ácido esteárico; ésteres de ácidos carboxílicos polivalentes, opcionalmente substituídos por hidróxi com álcoois graxos com 6 a 22 átomos de carbono, especialmente ésteres do ácido tartárico de cadeia longa; derivados de graxas e óleos, tais como, por exemplo, álcoois graxos, cetonas graxas, aldeídos graxos, éteres graxos e carbonatos graxos, que em soma apresentam pelo menos 24 átomos de carbono, especi- almente laurona e éter diestearílico; ácidos graxos, tais como ácido esteárico, ácido hidroxiesteárico ou ácido behênico, produtos de abertura de anel de peróxidos de olefinas com 12 a 22 átomos de carbono com álcoois graxos com 12 a 22 átomos de carbono e/ou polióis com 2 a 15 átomos de carbono e 2 a 10 grupos hidroxila e suas misturas.[0055] As pearl luster waxes are included, for example: alkylene glycol ester, especially ethylene glycol distearate; fatty acid alkanolamides, especially coconut fatty acid diethanolamide; partial glycerides, especially stearic acid monoglyceride; esters of polyvalent carboxylic acids, optionally substituted by hydroxy with fatty alcohols of 6 to 22 carbon atoms, especially long-chain tartaric acid esters; derivatives of greases and oils, such as, for example, fatty alcohols, fatty ketones, fatty aldehydes, fatty ethers and fatty carbonates, which in sum have at least 24 carbon atoms, especially laurone and distearyl ether; fatty acids such as stearic acid, hydroxystearic acid or behenic acid, ring-opening products of olefin peroxides of 12 to 22 carbon atoms with fatty alcohols of 12 to 22 carbon atoms and/or polyols of 2 to 15 carbon atoms carbon and 2 to 10 hydroxyl groups and mixtures thereof.
[0056] Agentes refrigerantes são compostos, que produzem uma sensação de frio na pele. Via de regra, trata-se, neste caso, de compostos de mentol, que - além do corpo de base o próprio mentol - por exemplo, selecionado a partir do grupo formado por éter metílico de mentol, mentona glicerol acetal (FEMA GRAS1 3807), mentona glicerol cetal (FEMA GRAS 3808), lactato de mentila (FEMA GRAS 3748), mentol etileno glicol carbonato (FEMA GRAS 3805), mentol propileno glicol carbonato (FEMA GRAS 3806), mentil-N-etiloxamato, succinato de monometila (FEMA GRAS 3810), glutamato de monomentila (FE- MA GRAS 4006), mentóxi-1,2-propanodiol (FEMA GRAS 3784), men- tóxi-2-metil-1,2-propanodioll (FEMA GRAS 3849) e os ésteres e ami- das de ácido mentanocarboxílico WS-3, WS-4, WS-5, WS-12, WS-14 e WS-30 e suas misturas.[0056] Cooling agents are compounds, which produce a cold sensation on the skin. As a rule, these are menthol compounds, which - in addition to the base body, menthol itself - for example, selected from the group formed by menthol methyl ether, menthone glycerol acetal (FEMA GRAS1 3807) , menthone glycerol ketal (FEMA GRAS 3808), menthyl lactate (FEMA GRAS 3748), menthol ethylene glycol carbonate (FEMA GRAS 3805), menthol propylene glycol carbonate (FEMA GRAS 3806), menthyl-N-ethyloxamate, monomethyl succinate (FEMA GRAS 3810), monomenthyl glutamate (FEMA GRAS 4006), menthoxy-1,2-propanediol (FEMA GRAS 3784), menthoxy-2-methyl-1,2-propanedioll (FEMA GRAS 3849) and the esters and Menthanecarboxylic acid amides WS-3, WS-4, WS-5, WS-12, WS-14 and WS-30 and mixtures thereof.
[0057] Um primeiro representante importante dessas substâncias é representado pelo succinato de monomentila (FEMA GRAS 3810). Tanto o succinato, como também o glutarato de monomentila análogo (FEMA GRAS 4006), representam representantes importantes de ésteres monomentílicos à base de ácidos di- e policarboxílicos (fórmula III): 1 FEMA representa "Flavor and Extracts Manufacturers Association" e GRAS é definido como "Generally Regarded As Safe". Uma designação FEMA GRAS significa, que a substância assim caracterizada é testada de acordo com o método padrão e é considerada como toxico- logicamente inofensiva. [0057] A first important representative of these substances is represented by monomenthyl succinate (FEMA GRAS 3810). Both succinate and analogous monomentyl glutarate (FEMA GRAS 4006) represent important representatives of monomentyl esters based on di- and polycarboxylic acids (formula III): 1 FEMA stands for "Flavor and Extracts Manufacturers Association" and GRAS is defined as "Generally Regarded As Safe". A FEMA GRAS designation means that the substance so characterized is tested according to the standard method and is considered to be toxicologically harmless.
[0058] Exemplos de aplicações dessas substâncias são encontra dos, por exemplo, nos impressos WO 2003 043431 (Unilever) ou EP 1332772 A1 (IFF).[0058] Examples of applications of these substances are found, for example, in WO 2003 043431 (Unilever) or EP 1332772 A1 (IFF).
[0059] O próximo grupo importante de compostos de mentol prefe ridos no sentido da invenção, compreende ésteres de carbonato de mentol e polióis, tais como, por exemplo, glicóis, glicerina ou carboidratos, tais como, por exemplo, etilenoglicol carbonatos de mentol (FEMA GRAS 3805 = Frescolat® MGC), propilenoglicol carbonatos de mentol (FEMA GRAS 3784 = Frescolat® MPC), 2-metil-1,2-propanodiol carbonatos de mentol (FEMA GRAS 3849) ou os derivados de açúcares correspondentes. Do mesmo modo, são preferidos os compostos de mentol lactato de metila (FEMA GRAS 3748 = Frescolat® ML) e, em particular, o mentona glicerol acetal (FEMA GRAS 3807) ou o mentona glicerol cetal (FEMA GRAS 3808), que é comercializado pelo nome Frescolat® MGA. Como particularmente vantajosos dentre essas subs-tâncias foram provados mentona glicerol acetal/cetal e o lactato de mentila e etileno glicol carbonato de mentol ou propileno glicol carbonato de mentol, que a requerente vendo pelos nomes Frescolat® MGA, Frescolat® ML, Frescolat® MGC e Frescolat® MPC.[0059] The next important group of preferred menthol compounds in the sense of the invention comprises menthol carbonate esters and polyols, such as, for example, glycols, glycerin or carbohydrates, such as, for example, menthol ethylene glycol carbonates ( FEMA GRAS 3805 = Frescolat® MGC), menthol propylene glycol carbonates (FEMA GRAS 3784 = Frescolat® MPC), menthol 2-methyl-1,2-propanediol carbonates (FEMA GRAS 3849) or the corresponding sugar derivatives. Likewise, methyl lactate menthol compounds (FEMA GRAS 3748 = Frescolat® ML) and, in particular, menthone glycerol acetal (FEMA GRAS 3807) or menthone glycerol ketal (FEMA GRAS 3808), which is commercially by the name Frescolat® MGA. As particularly advantageous among these substances, menthone glycerol acetal/ketal and menthyl lactate and ethylene glycol menthol carbonate or propylene glycol menthol carbonate, which the applicant sells under the names Frescolat® MGA, Frescolat® ML, Frescolat® MGC and Frescolat® MPC.
[0060] Nos anos 70 do século passado, foram desenvolvidos pri meiramente compostos de mentol, que na posição 3 dispõem de uma ligação C-C e dos quais, do mesmo modo, podem ser usados uma série de representantes. Essas substâncias são designadas, em geral, como tipos WS. O corpo de base é um derivado de mentol, no qual o grupo hidroxila é sub substituído um grupo carboxila (WS-1). Dessa estrutura derivam todos os outros tipos WS, tais como, por exemplo, as espécies preferidas WS-3, WS-4, WS-5, WS-12, WS-14 e WS-30.[0060] In the 70s of the last century, menthol compounds were first developed, which in the 3 position have a C-C bond and of which, in the same way, a series of representatives can be used. These substances are generally designated as WS types. The base body is a menthol derivative, in which the hydroxyl group is sub-substituted by a carboxyl group (WS-1). From this structure all other WS types are derived, such as, for example, the preferred species WS-3, WS-4, WS-5, WS-12, WS-14 and WS-30.
[0061] Como agentes que conferem consistência são incluídos, em primeira linha, os álcoois graxos ou álcoois hidroxigraxos com 12 a 22 e preferivelmente 16 a 18 átomos de carbono e, além disso, glicerí- deos parciais, ácidos graxos ou ácidos hidroxigraxos. Prefere-se uma combinação dessas substâncias com oligoglicosídeos de alquila e/ou N-metilglucamidas de ácido graxo com o mesmo comprimento de cadeia e/ou poliglicerinpoli-12-hidroxiestearatos. Espessantes adequados são, por exemplo, tipos de aerosila (ácidos silícicos hidrófilos), polissa- carídeos, em particular, goma xantana, guar-guar, agar-agar, alginatos e tiloses, carboximetilcelulose e hidroxietil- e hidroxipropilcelulose, além disso, mono- e diésteres de polietilenoglicol de peso molecular mais elevado de ácidos graxos, poliacrilatos (por exemplo, Carbopole® e tipos de pemulen da Goodrich; Synthalene® da Signa; tipos de keltrol da Kelco; tipos de sepigel da Seppic; tipos de salcare da Allied Col-loids), poliacrilamidas, polímeros, álcool polivinílico e polivinilpirrolido- na. Como particularmente eficazes foram provadas também as bento- nitas, tais como, por exemplo, Bentone® Gel VS-rPC (Rheox), no caso do qual se trata de uma mistura de ciclopentassiloxano, hectorita de diesteardimônio e propilenocarbonato. Outros agentes tensoativos incluídos, tais como, por exemplo, glicerídeos de ácidos graxos etoxila- dos, ésteres de ácidos graxos com polióis, tais como, por exemplo, pentaeritritol ou trimetilolpropano, etoxilatos de álcoois graxos com distribuição de homólogos estreitada ou oligoglicosídeos de alquila e ele- trólitos, tais como cloreto de sódio e cloreto de amônio.[0061] As consistency-giving agents, fatty alcohols or hydroxy fatty alcohols with 12 to 22 and preferably 16 to 18 carbon atoms are included, in the first place, and, in addition, partial glycerides, fatty acids or hydroxy fatty acids. A combination of these substances with alkyl oligoglycosides and/or fatty acid N-methylglucamides of the same chain length and/or polyglycerinpoly-12-hydroxystearates is preferred. Suitable thickeners are, for example, aerosyl types (hydrophilic silicic acids), polysaccharides, in particular xanthan gum, guar-guar, agar-agar, alginates and tyloses, carboxymethyl cellulose and hydroxyethyl- and hydroxypropyl cellulose, moreover, mono- and higher molecular weight polyethylene glycol diesters of fatty acids, polyacrylates (e.g. Carbopole® and pemulen grades from Goodrich; Synthalene® from Signa; keltrol grades from Kelco; sepigel grades from Seppic; salcare grades from Allied Col -loids), polyacrylamides, polymers, polyvinyl alcohol and polyvinylpyrrolidone. Bentonites, such as, for example, Bentone® Gel VS-rPC (Rheox), have also been proved to be particularly effective, in which case it is a mixture of cyclopentasiloxane, disteardimonium hectorite and propylene carbonate. Other surfactants included, such as, for example, glycerides of ethoxylated fatty acids, esters of fatty acids with polyols, such as, for example, pentaerythritol or trimethylolpropane, ethoxylates of fatty alcohols with narrow homolog distribution or alkyl oligoglycosides, and electrolytes such as sodium chloride and ammonium chloride.
[0062] Como agentes de re-engorduramento podem ser usadas substâncias, tais como, por exemplo, lanolina e lecitina e derivados de lanolina e lecitina polietoxilados ou acilados, ésteres de ácido poliol- graxo, monoglicerídeos e alcanolamidas de ácido graxo, sendo que as últimas servem ao mesmo tempo como estabilizadores de espuma.[0062] As re-greasing agents, substances such as, for example, lanolin and lecithin and polyethoxylated or acylated lanolin and lecithin derivatives, polyol-fatty acid esters, monoglycerides and fatty acid alkanolamides can be used, the the latter serve at the same time as foam stabilizers.
[0063] Como estabilizadores de espuma podem ser usados sais metálicos de ácidos graxos, tais como, por exemplo, estearato ou rici- noleato de magnésio, alumínio e/ou zinco.[0063] As foam stabilizers, metallic salts of fatty acids can be used, such as, for example, magnesium, aluminum and/or zinc stearate or ricinoleate.
[0064] Polímeros catiônicos adequados são, por exemplo, derivados de celulose catiônicos, tais como, por exemplo, uma hidroxietilce- lulose quaternária, que é vendida pelo nome Polymer JR 400® da Amerchol, amido catiônico, copolímeros de sais de dialquilamônio e acrilamidas, polímeros de vinilpirrolidona/vinilimidazol quaternário, tais como, por exemplo, Luviquat® (BASF), produtos de condensação de poliglicóis e aminas, polipeptídeos quaternários de colágeno, tais como, por exemplo, colágeno hidrolisado de lauryldimônio hidroxipropila (Lamequat®L/Grünau), polipeptídeos quaternários de trigo, polietile- noimina, polímeros catiônicos de silicone, tais como, por exemplo, amodimeticona, copolímeros do ácido adípico e dimetilaminohidroxi- propildietilenotriamina (Cartaretine®/Sandoz), copolímeros do ácido acrílico com cloreto de dimetil-dialilamônio (Merquat® 550/Chemviron), poliaminopoliamidas e seus polímeros hidrossolúveis reticulados, derivados de quitina catiônica, tais como, por exemplo, quitosana quaternária, opcionalmente distribuída em forma microcristalina, produtos de condensação de dihalogenoalquileno, tais como, por exemplo, dibro- mobutano com bisdialquilaminas, tais como, por exemplo, bis- dimetilamino-1,3-propano, goma guar catiônica, tal como, por exemplo, Jaguar® CBS, Jaguar® C-17, Jaguar® C-16 da empresa Celanese, polímeros de sal de amônio quaternário, tais como, por exemplo, Mira- pol® A-15, Mirapol® AD-1, Mirapol® AZ-1 da empresa Miranol.[0064] Suitable cationic polymers are, for example, cationic cellulose derivatives, such as, for example, a quaternary hydroxyethyl cellulose, which is sold under the name Polymer JR 400® by Amerchol, cationic starch, copolymers of dialkylammonium salts and acrylamides , quaternary vinylpyrrolidone/vinylimidazole polymers such as, for example, Luviquat® (BASF), condensation products of polyglycols and amines, quaternary collagen polypeptides, such as, for example, hydroxypropyl lauryldimonium hydrolyzed collagen (Lamequat®L/Grünau ), quaternary wheat polypeptides, polyethyleneimine, cationic silicone polymers such as, for example, amodimethicone, copolymers of adipic acid and dimethylaminohydroxypropyldiethylenetriamine (Cartaretine®/Sandoz), copolymers of acrylic acid with dimethyldiallylammonium chloride ( Merquat® 550/Chemviron), polyaminopolyamides and their cross-linked water-soluble polymers derived from cationic chitin, such as, for example, lo, quaternary chitosan, optionally distributed in microcrystalline form, condensation products of dihaloalkylene, such as, for example, dibromobutane with bisdialkylamines, such as, for example, bis-dimethylamino-1,3-propane, cationic guar gum, such as such as Jaguar® CBS, Jaguar® C-17, Jaguar® C-16 from the company Celanese, quaternary ammonium salt polymers, such as, for example, Mirapol® A-15, Mirapol® AD-1 , Mirapol® AZ-1 from the company Miranol.
[0065] Como polímeros aniônicos, bipolares, anfóteros e não ioni- cos são incluídos, por exemplo, copolímeros de acetato de vinila/ácido crotônico, copolímeros de vinilpirrolidona/acrilato de vinila, copolímeros de acetato de vinila/maleato de butila/acrilato de isobornila, copolíme- ros de éter metilvinílico/anidrido de ácido maleico e seus ésteres, ácidos poliacrílicos não reticulados e reticulados como polióis, copolíme- ros de cloreto de acrilamidopropiltrimetilamônio/acrilato, copolímeros de octilacrilamida/metacrilato de metila/metacrilato de terc.butilaminoetila/metacrilato de 2-hidroxipropila, polivinilpirrolidona, copolímeros de vinilpirrolidona/acetato de vinila, terpolímeros de vinil- pirrolidona/metacrilato de dimetilaminoetila/vinilcaprolactama e éteres de celulose opcionalmente derivatizados e silicones.[0065] As anionic, bipolar, amphoteric and nonionic polymers are included, for example, vinyl acetate/crotonic acid copolymers, vinylpyrrolidone/vinyl acrylate copolymers, vinyl acetate/butyl maleate/vinyl acrylate copolymers. isobornyl, methyl vinyl ether/maleic acid anhydride copolymers and esters thereof, uncrosslinked and crosslinked polyacrylic acids such as polyols, acrylamidopropyltrimethylammonium chloride/acrylate copolymers, octylacrylamide/methyl methacrylate/tert.butylaminoethyl methacrylate/ 2-hydroxypropyl methacrylate, polyvinylpyrrolidone, vinylpyrrolidone/vinyl acetate copolymers, vinylpyrrolidone/dimethylaminoethyl methacrylate/vinylcaprolactam terpolymers and optionally derivatized cellulose ethers and silicones.
[0066] Compostos de silicone adequados são, por exemplo, dime-tilpolissiloxano, metilfenilpolissiloxano, silicones cíclicos e compostos de silicone modificados com amino, ácido graxo, álcool, poliéter, epóxi, flúor, glicosídeo e/ou alquila, que à temperatura ambiente podem estar presentes tanto em forma líquida, como também em forma de resina. Além disso, são adequadas as simeticonas, no caso das quais se trata de misturas de dimeticonas com um comprimento de cadeia médio de 200 a 300 unidades de dimetilsiloxano e silicatos hidrogenados.[0066] Suitable silicone compounds are, for example, dimethylpolysiloxane, methylphenylpolysiloxane, cyclic silicones and silicone compounds modified with amino, fatty acid, alcohol, polyether, epoxy, fluorine, glycoside and/or alkyl, which at room temperature can be present both in liquid form and in resin form. Furthermore, simethicones are suitable, in which case they are mixtures of dimethicones with an average chain length of 200 to 300 dimethylsiloxane units and hydrogenated silicates.
[0067] Os umectantes servem para a otimização adicional das propriedades sensoriais da composição e para regular a umidade da pele. Ao mesmo tempo, a estabilidade ao frio das preparações de acordo com a invenção, em particular, no caso de emulsões, aumenta. Os umectantes estão geralmente contidos em uma quantidade de 0,1 a 15% em peso, preferivelmente 1 a 10% em peso e, em particular, 5 a 10% em peso.[0067] Humectants serve to further optimize the sensory properties of the composition and to regulate skin moisture. At the same time, the cold stability of the preparations according to the invention, in particular in the case of emulsions, increases. The humectants are generally contained in an amount of 0.1 to 15% by weight, preferably 1 to 10% by weight, and in particular 5 to 10% by weight.
[0068] De acordo com a invenção, são adequados entre outros os aminoácidos, ácido pirrolidonocarboxílico, ácido lático e sais dos mesmos, lactitol, ureia e derivados de ureia, ácido úrico, glicosamina, creatinina, produtos de dissociação do colágeno, quitosana ou sais/derivados de quitosana e, em particular, polióis e derivados de poliol (por exemplo, glicerina, diglicerina, triglicerina, etilenoglicol, pro- pilenoglicol, butilenoglicol, eritritol, 1,2,6-hexanotriol, polietilenoglicóis, tais como PEG-4, PEG-6, PEG-7, PEG-8, PEG-9, PEG-10, PEG-12, PEG-14, PEG-16, PEG-18, PEG-20), açúcares e derivados de açúcar (entre outros, frutose, glicose, maltose, maltitol, manitol, inositol, sorbitol, sorbitilsilanodiol, sucrose, trehalose, xilose, xilitol, ácido glucurôni- co e sais dos mesmos), sorbitol etoxilado (Sorbeth-6, Sorbeth-20, Sor- beth-30, Sorbeth-40), mel e mel solidificado, hidrolisados de amido solidificado e misturas de proteína do trigo solidificada e copolímero de acetato de PEG-20. De acordo com a invenção, como umectantes são preferivelmente adequados a glicerina, diglicerina, triglicerina e butile- noglicol.[0068] According to the invention, among others, amino acids, pyrrolidonecarboxylic acid, lactic acid and salts thereof, lactitol, urea and urea derivatives, uric acid, glucosamine, creatinine, collagen dissociation products, chitosan or salts are suitable. /chitosan derivatives and in particular polyols and polyol derivatives (e.g. glycerin, diglycerin, triglycerin, ethylene glycol, propylene glycol, butylene glycol, erythritol, 1,2,6-hexanetriol, polyethylene glycols such as PEG-4, PEG-6, PEG-7, PEG-8, PEG-9, PEG-10, PEG-12, PEG-14, PEG-16, PEG-18, PEG-20), sugars and sugar derivatives (among others, fructose, glucose, maltose, maltitol, mannitol, inositol, sorbitol, sorbitylsilanediol, sucrose, trehalose, xylose, xylitol, glucuronic acid and salts thereof), ethoxylated sorbitol (Sorbeth-6, Sorbeth-20, Sorbeth-30 , Sorbeth-40), honey and solidified honey, solidified starch hydrolysates and mixtures of solidified wheat protein and PEG-acetate copolymer 20. According to the invention, glycerin, diglycerin, triglycerin and butylene glycol are preferably suitable as humectants.
[0069] Por substâncias biogênicas ativas devem ser entendidos,por exemplo, tocoferol, acetato de tocoferol, palmitato de tocoferol, ácido ascórbico, ácido (desóxi)ribonucleico e seus produtos de fragmentação, β-glucanos, retinol, bisabolol, alantoína, fitanotriol, pantenol, ácidos AHA, aminoácidos, ceramidas, pseudoceramidas, óleos essenciais, extratos de plantas, tais como, por exemplo, extrato de Prunus, extrato de noz de Vigna subterrânea e complexos de vitamina.[0069] By biogenic active substances should be understood, for example, tocopherol, tocopheryl acetate, tocopheryl palmitate, ascorbic acid, (deoxy)ribonucleic acid and its fragmentation products, β-glucans, retinol, bisabolol, allantoin, phytanotriol, panthenol, AHA acids, amino acids, ceramides, pseudoceramides, essential oils, plant extracts such as, for example, Prunus extract, underground Vigna nut extract and vitamin complexes.
[0070] Os antioxidantes interrompem a cadeia de reação fotoquí- mica, que é causada, quando a radiação UV penetra na pele. Exemplos típicos desses são os aminoácidos (por exemplo, glicina, histidina, tirosina, triptofano) e seus derivados, imidazóis (por exemplo, ácido urocânico) e seus derivados, peptídeos, tais como D,L-carnosina, D- carnosina, L-carnosina e seus derivados (por exemplo, anserina), ca- rotinóides, carotinas (por exemplo, α-carotina, β-carotina, licopina) e seus derivados, ácido clorogênico e seus derivados, ácido lipônico e seus derivados (por exemplo, ácido di-hidrolipônico), aurotioglicose, propiltiouracila e outros tióis (por exemplo, tioredoxina, glutation, ciste- ína, cistina, cistamina e seus ésteres de glicosila, N-acetila, metílico, etílico, propílico, amílico, butílico e láurico, de palmitoila, oleila, Y- linoleila, colesterol e glicérico) e sais dos mesmos, tiodipropionato de dilaurila, tiodipropionato de diestearila, ácido tiodipropiônico e seus derivados (éster, éter, peptídeos, lipídeos, nucleotídeos, nucleosídeos e sais) e compostos de sulfoximina (por exemplo, sulfoximinas de butio- nina, sulfoximina de homocisteína, sulfonas de butionina, sulfoximina de penta-, hexa-, heptationina) em dosagens compatíveis muito baixas (por exemplo, pmol até μmol/kg), além disso, quelatores (de metal) (por exemplo, ácidos α-hidroxigraxos, ácido palmítico, ácido fitínico, lactoferrina), a-hidroxiácidos (por exemplo, ácido cítrico, ácido lático, ácido málico), ácido humínico, ácido galênico, extratos de galeno, bilir- rubina, biliverdina, EDTA, EGTA e seus derivados, ácidos graxos insa- turados e seus derivados (por exemplo, ácido Y-linolênico, ácido linóli- co, ácido oleico), ácido fólico e seus derivados, ubiquinona e ubiquinol e seus derivados, vitamina C e derivados (por exemplo, palmitato de ascorbila, ascorbilfosfato de Mg, acetato de ascorbila), tocoferóis e derivados (por exemplo, acetato de vitamina E), vitamina A e derivados (palmitato de vitamina A) e benzoato de coniferila da resina benzóica, ácido rutínico e seus derivados, α-glicosilrutina, ácido ferúlico, furfurili- denoglucitol, carnosina, butil-hidroxitolueno, butil-hidroxianisol, ácido nordi-hidroguajac-resinóico, ácido nordi-hidroguajarrético, tri- hidroxibutirofenona, ácido úrico e seus derivados, manose e seus deri-vados, superóxido dismutase, zinco e seus derivados (por exemplo, ZnO, ZnSO4), selênio e seus derivados (por exemplo, selênio- metionina), estilbenos e seus derivados (por exemplo, óxido de estil- beno, óxido de trans-estilbeno) e os derivados adequados de acordo com a invenção (sais, ésteres, éteres, açúcar, nucleotídeos, peptídeos e lipídeos) dessas substâncias ativas mencionadas.[0070] Antioxidants interrupt the photochemical reaction chain, which is caused when UV radiation penetrates the skin. Typical examples of these are amino acids (e.g. glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles (e.g. urocanic acid) and their derivatives, peptides such as D,L-carnosine, D-carnosine, L- carnosine and its derivatives (e.g. anserine), carotinoids, carotins (e.g. α-carotene, β-carotene, lycopine) and its derivatives, chlorogenic acid and its derivatives, liponic acid and its derivatives (e.g. dihydroliponic), aurothioglucose, propylthiouracil and other thiols (e.g. thioredoxin, glutathione, cysteine, cystine, cystamine and their glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauric esters of palmitoyl , oleyl, Y-linoleyl, cholesterol and glycerol) and salts thereof, dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and its derivatives (ester, ether, peptides, lipids, nucleotides, nucleosides and salts) and sulfoximine compounds (eg example, sulfoximines of butionine, homocysteine sulfoximine, butionine sulfones, penta-, hexa-, heptathionine sulfoximine) in very low compatible dosages (e.g. pmol up to μmol/kg), in addition, (metal) chelators (e.g. , α-hydroxy fatty acids, palmitic acid, phytinic acid, lactoferrin), α-hydroxy acids (e.g. citric acid, lactic acid, malic acid), huminic acid, galenic acid, galene extracts, bilirubin, biliverdin, EDTA, EGTA and its derivatives, unsaturated fatty acids and their derivatives (e.g. Y-linolenic acid, linolic acid, oleic acid), folic acid and their derivatives, ubiquinone and ubiquinol and their derivatives, vitamin C and derivatives (e.g. e.g. ascorbyl palmitate, Mg ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives (e.g. vitamin E acetate), vitamin A and derivatives (vitamin A palmitate) and benzoic resin coniferyl benzoate, rutinic acid and its derivatives, α-glycosylrutin, ferulic acid, f urfurylideneglucitol, carnosine, butylhydroxytoluene, butylhydroxyanisole, nordihydroguajac-resinoic acid, nordihydroguajarretic acid, trihydroxybutyrophenone, uric acid and its derivatives, mannose and its derivatives, superoxide dismutase, zinc and its derivatives (e.g. ZnO, ZnSO4), selenium and its derivatives (e.g. selenium-methionine), stilbenes and their derivatives (e.g. stilbene oxide, trans-stilbene oxide) and suitable derivatives according to invention (salts, esters, ethers, sugar, nucleotides, peptides and lipids) of these active substances mentioned.
[0071] Desodorantes cosméticos (desodorantes) reagem contra odores corporais, mascaram ou afastam os mesmos. Os odores corporais resultam através da ação de bactérias da pele sobre o suor apó- crino, formando-se produtos de degradação de odor desagradável. Portanto, os desodorantes contêm substâncias ativas, que atuam como agentes inibidores de germes, inibidores de enzimas, absorvedo- res de odor ou mascaradores de odor.[0071] Cosmetic deodorants (deodorants) react against body odors, mask or remove them. Body odors result from the action of skin bacteria on apocrine sweat, forming unpleasant odor degradation products. Therefore, deodorants contain active substances, which act as germ-inhibiting agents, enzyme inhibitors, odor absorbers or odor masking agents.
[0072] Como agentes inibidores de germes são fundamentalmente adequadas todas as substâncias eficazes contra bactérias gram- positivas, tais como, por exemplo, ácido 4-hidroxibenzóico e sais dos mesmos e ésteres, N-(4-clorofenil)-N’-(34-diclorofenil)ureia, éter 2,4,4’- tricloro-2’-hidróxi-difenílico (triclosan), 4-cloro-3,5-dimetil-fenol, 2,2’- metilen-bis(6-bromo-4-clorofenol), 3-metil-4-(1-metiletil)-fenol, 2-benzil- 4-clorofenol, 3-(4-clorofenóxi)-1,2-propanodiol, 3-iodo-2-propinilbutilcarbamato, clorhexidina, 3,4,4’-triclorocarbanilida (TTC), fragrâncias antibacterianas, timol, óleo de tomilho, eugenol, óleo de cravo, mentol, óleo de hortelã, farnesol, fenoxietanol, monocaprinato de glicerina, monocaprilato de glicerina, monolaurato de glicerina (GML), monocaprinato de diglicerina (DMC), N-alquilamidas de ácido salicílico, tais como, por exemplo, n-octilamida de ácido salicílico ou n- decilamida de ácido salicílico.[0072] Essentially all substances effective against gram-positive bacteria are suitable as germ-inhibiting agents, such as, for example, 4-hydroxybenzoic acid and salts thereof and esters, N-(4-chlorophenyl)-N'-( 34-dichlorophenyl)urea, 2,4,4'-trichloro-2'-hydroxy-diphenyl ether (triclosan), 4-chloro-3,5-dimethyl-phenol, 2,2'-methylene-bis(6-bromo) -4-chlorophenol), 3-methyl-4-(1-methylethyl)-phenol, 2-benzyl-4-chlorophenol, 3-(4-chlorophenoxy)-1,2-propanediol, 3-iodo-2-propynylbutylcarbamate, chlorhexidine, 3,4,4'-trichlorocarbanilide (TTC), antibacterial fragrances, thymol, thyme oil, eugenol, clove oil, menthol, peppermint oil, farnesol, phenoxyethanol, glycerin monocaprinate, glycerin monocaprylate, glycerin monolaurate (GML), diglycerin monocaprinate (DMC), salicylic acid N-alkylamides such as, for example, salicylic acid n-octylamide or salicylic acid n-decylamide.
[0073] Como inibidores de enzima são adequados, por exemplo,os inibidores de esterase. Aqui, trata-se preferivelmente de citratos de trialquila, tais como citrato de trimetila, citrato de tripropila, citrato de triisopropila, citrato de tributila e, em particular, de citrato de trietila (Hydagen® CAT). As substâncias inibem a atividade enzimática e reduzem, assim, a formação de odor. Outras substâncias, que são incluídas como inibidores de esterase, são sulfatos ou fosfatos de esterol, tais como, por exemplo, sulfato ou fosfato de lanosterina, colesterina, campesterina, estigmasterina e sitoesterina, ácidos dicarboxílicos e seus ésteres, tais como, por exemplo, ácido glutárico, éster monoetíli- co de ácido glutárico, éster dietílico de ácido glutárico, ácido adípico, éster monoetílico de ácido adípico, éster dietílico de ácido adípico, ácido malônico e éster dietílico de ácido malônico, ácidos hidroxicarboxí- licos e seus ésteres, tais como, por exemplo, ácido cítrico, ácido máli- co, ácido tartárico ou éster dietílico de ácido tartárico e glicinato de zinco.[0073] As enzyme inhibitors, for example, esterase inhibitors are suitable. Here, they are preferably trialkyl citrates, such as trimethyl citrate, tripropyl citrate, triisopropyl citrate, tributyl citrate and, in particular, triethyl citrate (Hydagen® CAT). The substances inhibit enzymatic activity and thus reduce odor formation. Other substances, which are included as esterase inhibitors, are sterol sulfates or phosphates, such as, for example, lanosterine sulfate or phosphate, cholesterine, campesterine, stigmasterine and sitosterin, dicarboxylic acids and their esters, such as, for example, glutaric acid, glutaric acid monoethyl ester, glutaric acid diethyl ester, adipic acid, adipic acid monoethyl ester, adipic acid diethyl ester, malonic acid and malonic acid diethyl ester, hydroxycarboxylic acids and their esters, such as such as, for example, citric acid, malic acid, tartaric acid or diethyl ester of tartaric acid and zinc glycinate.
[0074] Como absorvedores de odor são adequadas substâncias,que absorvem os compostos formadores de odor e que podem reter os mesmos amplamente. Esses diminuem a pressão parcial dos componentes isolados e reduzem, assim, também sua velocidade de propagação. É importante, que neste caso os perfumes devem permanecer inalterados. Os absorvedores de odor não têm qualquer eficácia contra bactérias. Esses contêm, por exemplo, como componente principal um sal de zinco complexo do ácido ricinoleico ou fragrâncias especiais, de odor amplamente neutro, que são conhecidos pelo especialista como “fixadores”, tais como, por exemplo, extratos de Labdanum ou Styrax ou certos derivados de ácido abiético. Como mascaradores de odor atuam odorizantes ou óleos de perfume, que adicionalmente à sua função como mascaradores de odor conferem aos desodorantes sua respectiva nota olfativa. Como óleos de perfume sejam mencionadas, por exemplo, misturas de odorizantes naturais e sintéticas. Odorizan- tes naturais são extratos de flores, hastes e folhas, frutas, cascas de frutas, raízes, madeiras, ervas e gramas, agulhas e ramos e resinas e bálsamos. Além disso, são incluídas matérias-primas animais, tais como, por exemplo, almíscar e castoreum. Compostos odorizantes sintéticos típicas são produtos do tipo dos ésteres, éteres, aldeídos, ceto- nas, álcoois e hidrocarbonetos. Compostos odorizantes do tipo dos ésteres são, por exemplo, acetato de benzila, acetato de p-terc.- butilciclo-hexila, acetato de linalila, acetato de feniletila, benzoato de linalila, formiato de benzila, propionato de alilciclo-hexila, propionato de estiralila e salicilato de benzila. Os éteres incluem, por exemplo, o éter benziletílico, nos aldeídos, por exemplo, os alcanais lineares com 8 a 18 átomos de carbono, citral, citronelal, citroneliloxiacetaldeído, aldeído ciclamen, hidroxicitronelal, lilial e bourgeonal, nas cetonas, por exemplo, as jojonas e metilcedrilcetona, nos álcoois o anetol, citrone- lol, eugenol, isoeugenol, geraniol, linalol, álcool feniletílico e terpineol, os hidrocarbonetos incluem principalmente os terpenos e bálsamos. Preferivelmente, contudo, são usadas misturas de vários odorizantes, que produzem conjuntamente uma nota olfativa atraente. Também óleos etéreos de volatilidade relativamente baixa, que são usados na maioria das vezes como componentes aromáticos, são adequados como óleos de perfume, por exemplo, óleo de salva, óleo de camomila, óleo de cravo, óleo de melissa, óleo de hortelã, óleo de folhas de canela, óleo de tília, óleo de bagas de zimbro, óleo de vetiver, óleo de olíbano, óleo de ferula gumosa, óleo de labdanum e óleo de lavandim. Preferivelmente, são usados o óleo de bergamota, di-hidromircenol, lilial, liral, citronelol, álcool feniletílico, aldeído cinâmico de α-hexila, geraniol, benzilacetona, ciclamenaldeído, linalol, Boisambrene Forte, ambroxano, indol, hediona, sandelice, óleo de limão, óleo de tangerina, óleo de laranja, glicolato de alilamila, ciclovertal, óleo de lavandim, óleo de salva de uva, β-damasco, óleo de uisque de gerânio, salicilato de ciclo-hexila, vertofix coeur, iso-E-super, Fixolide NP, evernila, iral- deina gama, ácido fenilacético, acetato de geranila, acetato de benzila, óxido de rosa, romilato, irotila e floramato isolados ou em misturas.[0074] Substances which absorb the odor-forming compounds and which can retain them widely are suitable as odor absorbers. These decrease the partial pressure of the isolated components and thus also reduce their propagation speed. It is important, that in this case the perfumes must remain unchanged. Odor absorbers are not effective against bacteria. These contain, for example, as a main component a complex zinc salt of ricinoleic acid or special fragrances, with a largely neutral odor, which are known to the expert as “fixers”, such as, for example, extracts of Labdanum or Styrax or certain derivatives. of abietic acid. Odorants or perfume oils act as odor maskers, which, in addition to their function as odor maskers, give deodorants their respective olfactory note. As perfume oils, for example, mixtures of natural and synthetic odorants are mentioned. Natural odorants are extracts from flowers, stems and leaves, fruits, fruit peels, roots, woods, herbs and grasses, needles and branches and resins and balms. In addition, animal raw materials such as, for example, musk and castoreum are included. Typical synthetic odorant compounds are esters, ethers, aldehydes, ketones, alcohols and hydrocarbons. Flavor compounds of the ester type are, for example, benzyl acetate, p-tert-butylcyclohexyl acetate, linalyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, allylcyclohexyl propionate, styralyl and benzyl salicylate. Ethers include, for example, benzylethyl ether, in aldehydes, for example, linear alkanals of 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilyal and bourgeonal, in ketones, for example, jojonas and methylcedrylketone, in alcohols anethole, citronellol, eugenol, isoeugenol, geraniol, linalool, phenylethyl alcohol and terpineol, hydrocarbons mainly include terpenes and balms. Preferably, however, mixtures of various odorants are used, which together produce an attractive olfactory note. Also relatively low volatility ethereal oils, which are used most often as aromatic components, are suitable as perfume oils, e.g. sage oil, chamomile oil, clove oil, lemon balm oil, peppermint oil, cinnamon leaf oil, linden oil, juniper berry oil, vetiver oil, frankincense oil, ferula gumosa oil, labdanum oil and lavandin oil. Preferably, bergamot oil, dihydromyrcenol, lilyl, lyral, citronellol, phenylethyl alcohol, α-hexyl cinnamic aldehyde, geraniol, benzylacetone, cyclamenaldehyde, linalool, Boisambrene Forte, ambroxane, indole, hedione, sandelice, oil of lemon, tangerine oil, orange oil, allylamyl glycolate, cyclovertal, lavandin oil, grape sage oil, β-apricot, geranium whiskey oil, cyclohexyl salicylate, vertofix coeur, iso-E-super , Fixolide NP, evernyl, iraldein gamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, romilate, irotyl and floramate alone or in mixtures.
[0075] Os antitranspirantes (antiperspirantes) reduzem, através da influência da atividade das glândulas sudoríparas ecrinas, a formação de suor e, dessa maneira, reagem contra a umidade das axilas e odor corporal. Formulações aquosas ou anidras de antitranspirantes contêm tipicamente as seguintes substâncias constitutivas: • substâncias ativas adstringentes, • componentes oleosos, • emulsificantes não iônicos, • coemulsificantes, • agentes que conferem consistência, • substâncias auxiliares, tais como, por exemplo, espes- santes ou agentes de complexação e/ou • solventes não aquosos, tais como, por exemplo, etanol, propilenoglicol e/ou glicerina.[0075] Antiperspirants (antiperspirants) reduce, through the influence of the activity of the eccrine sweat glands, the formation of sweat and thus react against underarm dampness and body odor. Aqueous or anhydrous formulations of antiperspirants typically contain the following constituents: • astringent active substances, • oil components, • non-ionic emulsifiers, • co-emulsifiers, • consistency-giving agents, • auxiliary substances such as, for example, thickeners or complexing agents and/or • non-aqueous solvents, such as, for example, ethanol, propylene glycol and/or glycerin.
[0076] Como substâncias ativas antitranspirantes adstringentes são adequados principalmente sais do alumínio, zircônio ou do zinco. Tais substâncias ativas de ação antiperspirante adequadas são, por exemplo, cloreto de alumínio, cloridrato de alumínio, diclorohidrato de alumínio, sesquicloridrato de alumínio e seus compostos complexos, por exemplo, com propilenoglicol-1,2. Hidroxialantoinato de alumínio, tartrato de cloreto de alumínio, tricloridrato de alumínio-zircônio, te- tracloridrato de alumínio-zircônio, pentacloridrato de alumínio-zircônio e seus compostos complexos, por exemplo, com aminoácidos, tais como glicina. Além disso, nos antitranspirantes podem estar contidos agentes auxiliares solúveis em óleo e hidrossolúveis usuais em menores quantidades. Tais agentes auxiliares solúveis em óleo podem ser, por exemplo: • óleos etéreos anti-inflamatórios, protetores da pele ou perfumados, substâncias ativas sintéticas, protetoras da pele e/ou • óleos de perfume solúveis em óleo.[0076] As astringent antiperspirant active substances, mainly aluminum, zirconium or zinc salts are suitable. Such suitable antiperspirant active substances are, for example, aluminum chloride, aluminum hydrochloride, aluminum dichlorohydrate, aluminum sesquihydrochloride and their complex compounds, for example with propylene glycol-1,2. Aluminum hydroxyalantoinate, aluminum chloride tartrate, aluminum zirconium trihydrochloride, aluminum zirconium tetrahydrochloride, aluminum zirconium pentahydrochloride and their complex compounds, eg with amino acids such as glycine. In addition, the usual oil-soluble and water-soluble auxiliary agents may be contained in the antiperspirants in smaller amounts. Such oil-soluble auxiliary agents may be, for example: • anti-inflammatory, skin-protective or scented ethereal oils, synthetic, skin-protective active substances and/or • oil-soluble perfume oils.
[0077] Aditivos hidrossolúveis usuais são, por exemplo, conser vantes, odorizantes hidrossolúveis, agentes de ajuste do valor de pH, por exemplo, misturas tampão, espessantes hidrossolúveis, por exemplo, polímeros naturais ou sintéticos hidrossolúveis, tais como, por exemplo, goma xantana, hidroxietilcelulose, polivinilpirrolidona ou óxidos de polietileno de peso molecular elevado.[0077] Usual water-soluble additives are, for example, preservatives, water-soluble odorants, pH-adjusting agents, for example, buffer mixtures, water-soluble thickeners, for example, water-soluble natural or synthetic polymers, such as, for example, gum xanthan, hydroxyethylcellulose, polyvinylpyrrolidone or high molecular weight polyethylene oxides.
[0078] Como repelentes de insetos são incluídos N,N-dietil-m- toluamida, 1,2-pentanodiol ou butilacetilaminopropionatos de etila.[0078] As insect repellents are included N,N-diethyl-m-toluamide, 1,2-pentanediol or ethyl butylacetylaminopropionates.
[0079] Como autobronzeadores é adequada a di-hidroxiacetona. Como inibidores de tirosina, que impedem a formação de melamina e encontram aplicação em agentes de despigmentação, são incluídos, por exemplo, a arbutina, ácido ferúlico, ácido koji, ácido cumárico e ácido ascórbico (vitamina C).[0079] Dihydroxyacetone is suitable as self-tanning products. As tyrosine inhibitors which prevent melamine formation and find application in depigmentation agents, for example arbutin, ferulic acid, koji acid, coumaric acid and ascorbic acid (vitamin C) are included.
[0080] Além disso, para melhorar o comportamento de fluidez, podem ser usados hidrótropos, tais como, por exemplo, etanol, álcool isopropílico ou polióis; essas substâncias correspondem amplamente aos veículos descritos no início. Os polióis, que são incluídos aqui, possuem preferivelmente 2 a 15 átomos de carbono e pelo menos dois grupos hidroxila. Os polióis podem conter ainda outros grupos funcionais, em particular, grupos amino ou ser modificados com nitrogênio. Exemplos típicos são • glicerina; • alquilenoglicóis, tais como, por exemplo, etilenoglicol, die- tilenoglicol, propilenoglicol, butilenoglicol, hexilenoglicol e polietileno- glicóis com um peso molecular médio de 100 a 1.000 Dalton; • misturas técnicas de oligoglicerina com um grau de con-densação próprio de 1,5 a 10, tal como misturas técnicas de diglicerina com um teor de diglicerina de 40 a 50% em peso; • compostos de metilol, tais como, em particular, trimetilole- tano, trimetilolpropano, trimetilolbutano, pentaeritritol e dipentaeritritol; • alquilglicosídeos inferiores, em particular, aqueles com 1 a 8 átomos de carbono no radical alquila, tais como por exemplo, me- til- e butilglicosídeo; • álcoois de açúcar com 5 a 12 átomos de carbono, tais como, por exemplo, sorbitol ou manitol; • açúcar com 5 a 12 átomos de carbono, tal como, por exemplo, glicose ou sacarose; • amino açúcar, tal como, por exemplo, glucamina; • aminas de diálcool, tais como dietanolamina ou 2-amino- 1,3-propanodiol.[0080] Furthermore, to improve the flow behavior, hydrotropes can be used, such as, for example, ethanol, isopropyl alcohol or polyols; these substances largely correspond to the vehicles described at the beginning. The polyols, which are included herein, preferably have 2 to 15 carbon atoms and at least two hydroxyl groups. Polyols may contain further functional groups, in particular amino groups or be modified with nitrogen. Typical examples are • glycerin; • alkylene glycols, such as, for example, ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, hexylene glycol and polyethylene glycols having an average molecular weight of 100 to 1000 Daltons; • technical oligoglycerin mixtures with a proper degree of condensation of 1.5 to 10, such as technical diglycerin mixtures with a diglycerin content of 40 to 50% by weight; • methylol compounds, such as, in particular, trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol and dipentaerythritol; • lower alkylglycosides, in particular those with 1 to 8 carbon atoms in the alkyl moiety, such as, for example, methyl- and butylglycoside; • sugar alcohols with 5 to 12 carbon atoms, such as, for example, sorbitol or mannitol; • sugar with 5 to 12 carbon atoms, such as, for example, glucose or sucrose; • amino sugar, such as, for example, glucamine; • dialcohol amines such as diethanolamine or 2-amino-1,3-propanediol.
[0081] Como conservantes são adequados, por exemplo, o fenoxi-etanol, solução de formaldeído, parabenos, pentanodiol ou ácido sór- bico e os complexos de prata conhecidos pelo nome Surfacine® e as outras classes de substâncias listadas no anexo 6, parte A e B do regulamento de cosméticos.[0081] Suitable preservatives include, for example, phenoxy-ethanol, formaldehyde solution, parabens, pentanediol or sorbic acid and the silver complexes known by the name Surfacine® and the other classes of substances listed in Annex 6, part A and B of the cosmetics regulation.
[0082] Como óleos de perfume sejam mencionadas as misturas de odorizantes. Odorizantes naturais são extratos de flores (lírio, lavanda, rosas, jasmim, néroli, ylang-ylang), caules e folhas (gerânio, patchouli, petitgrain), frutas (anis, coentro, cominho, zimbro), cascas de frutas (bergamota, limão, laranjas), raízes (noz moscada, angélica, aipo, car- damomo, costus, íris, açoro), madeiras (madeira de pinho, sândalo, gaja, cedro, rosa), ervas e gramíneas (estragão, capim limão, salva, tomilho), agulhas e ramos (abeto, pinheiro, pinheiro bravo, pinheiro da montanha), resinas e bálsamos (gálbano, elemi, benzoína, mirra, olí- bano, opoponax). Além disso, são incluídos odorizantes animais, tais como, por exemplo, civeta e castóreo). Compostos odorizantes sintéticos típicos são produtos do tipo dos ésteres, éteres, aldeídos, cetonas, álcoois e hidrocarbonetos. Compostos odorizantes do tipo dos ésteres são, por exemplo, acetato de benzila, fenoxietilisobutirato, acetato de p-terc.-butilciclo-hexila, acetato de linalila, acetato de dimetilbenzilcar- binila, acetato de feniletila, benzoato de linalina, formiato de benzila, glicinato de etilmetilfenila, propionato de alilciclo-hexila, propionato de estiralila e salicilato de benzila. Nos éteres são incluídos, por exemplo, éter benziletílico, nos aldeídos, por exemplo, os alcanais lineares com 8 a 18 átomos de carbono, citral, citronelal, citroneliloxiacetaldeído, aldeído ciclamen, hidroxicitronelal, lilial e bourgeonal, nas cetonas, por exemplo, as jojonas, α-isometilionona e metilcedrilcetona, nos álcoois o anetol, citronelol, eugenol, isoeugenol, geraniol, linalol, álcool fetiletí- lico e terpineol, aos hidrocarbonetos pertencem principalmente os ter- penos e bálsamos. Preferivelmente, contudo, são usadas misturas de vários odorizantes, que conjuntamente produzem uma nota olfativa atraente. Também óleos etéreos de menor volatilidade, que na maioria das vezes são usados como componentes aromáticos, são adequados como óleos de perfume, por exemplo, óleo de salva, óleo de camomila, óleo de cravos, óleo de melissa, óleo de hortelã, óleo de folhas de canela, óleo de flor de tília, óleo de baga de zimbro, óleo de vetiver, óleo de olíbano, óleo de ferula gumosa, óleo de labolanum e óleo de lavandim. Preferivelmente, o óleo de bergamota, di-hidromircenol, lilial, liral, citronelol, álcool feniletílico, aldeído a-hexilcinâmico, geraniol, benzilacetona, aldeído ciclamen, linalol, Boisambrene Forte, ambro- xan, indol, hediona, sandelice, óleo de limão, óleo de tangerina, óleo de laranja, glicolato de alilamila, ciclovertal, óleo de lavandim, óleo de salva de uva, β-damasco, óleo de uisque de gerânio, salicilato de ciclo-hexila, vertofix coeur, iso-E-Super, Fixolide NP, evernila, iraldeída gama, ácido fenilacético, acetato de geranila, acetato de benzila, óxido de rosa, romilato, irotila e floramato isolados ou em misturas.[0082] As perfume oils, mixtures of odorants are mentioned. Natural fragrances are extracts of flowers (lily, lavender, roses, jasmine, neroli, ylang-ylang), stems and leaves (geranium, patchouli, petitgrain), fruits (anise, coriander, cumin, juniper), fruit peels (bergamot, lemon, oranges), roots (nutmeg, angelica, celery, cardamom, costus, iris, azorean), woods (pine wood, sandalwood, gaja, cedar, rose), herbs and grasses (tarragon, lemongrass, sage , thyme), needles and branches (fir, pine, maritime pine, mountain pine), resins and balms (galbanum, elemi, benzoin, myrrh, frankincense, opoponax). In addition, animal odorants such as, for example, civet and castoreum are included). Typical synthetic odorant compounds are products such as esters, ethers, aldehydes, ketones, alcohols and hydrocarbons. Flavor compounds of the ester type are, for example, benzyl acetate, phenoxyethylisobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linaline benzoate, benzyl formate, ethylmethylphenyl glycinate, allylcyclohexyl propionate, styralyl propionate and benzyl salicylate. Ethers include, for example, benzylethyl ether, aldehydes, for example, linear alkanals with 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilyal and bourgeonal, and ketones, for example, jojonas, α-isomethylionone and methylcedrylketone, in alcohols anethole, citronellol, eugenol, isoeugenol, geraniol, linalool, fetylethyl alcohol and terpineol, the hydrocarbons mainly include terpenes and balms. Preferably, however, mixtures of various odorants are used, which together produce an attractive olfactory note. Also ethereal oils of lower volatility, which are most often used as aromatic components, are suitable as perfume oils, e.g. sage oil, chamomile oil, clove oil, lemon balm oil, peppermint oil, cinnamon leaves, linden blossom oil, juniper berry oil, vetiver oil, frankincense oil, ferula gumosa oil, labolanum oil and lavandim oil. Preferably, bergamot oil, dihydromyrcenol, lilyl, lyral, citronellol, phenylethyl alcohol, a-hexylcinnamic aldehyde, geraniol, benzylacetone, cyclamen aldehyde, linalool, Boisambrene Forte, ambroxan, indole, hedione, sandelice, lemon oil , tangerine oil, orange oil, allylamyl glycolate, cyclovertal, lavandin oil, grape sage oil, β-apricot, geranium whiskey oil, cyclohexyl salicylate, vertofix coeur, iso-E-Super, Fixolide NP, evernyl, gamma iraldehyde, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, romilate, irotile and floramate alone or in mixtures.
[0083] Como aromas são incluídos, por exemplo, óleo de hortelã-pimenta, óleo de hortelã crespa, óleo de anis, óleo de estrela de anis, óleo de cominho, óleo de eucalipto, óleo de funcho, óleo de limão, óleo de gaultéria, óleo de cravo, mentol e similares.[0083] As flavorings are included, for example, peppermint oil, curly spearmint oil, anise oil, star anise oil, cumin oil, eucalyptus oil, fennel oil, lemon oil, wintergreen, clove oil, menthol and the like.
[0084] Como corantes podem ser usadas as substâncias acessí veis e adequadas para fins cosméticos, tais como são compiladas na publicação “Kosmetische Farbemitte” da Farbstoffkommission der Deutschen Forschungsgemeinschaft, Verlag Chemie, Weinheim, 1984, página 81-106. Exemplos são vermelho cochonilha A (C.I. 16255), azul patente V (C.I.42051), indigotin (C.I.73015), clorofilina (C.I.75810), amarelo quinolina (C.I.47005), dióxido de titânio (C.I.77891), azul indantreno RS (C.I.69800) e laca ruiva (C.I.58000). Como corante de luminescência também pode estar contido o luminol. Esses corantes são geralmente usados em concentrações de 0,001 a 0,1% em peso, com base em toda a mistura.[0084] As colorants, substances accessible and suitable for cosmetic purposes can be used, such as are compiled in the publication “Kosmetische Farbemitte” of the Farbstoffkommission der Deutschen Forschungsgemeinschaft, Verlag Chemie, Weinheim, 1984, page 81-106. Examples are cochineal red A (CI 16255), patent blue V (CI42051), indigotin (CI73015), chlorophyllin (CI75810), quinoline yellow (CI47005), titanium dioxide (CI77891), indanthrene blue RS (CI 69800) and red lacquer (CI58000). As a luminescence dye, luminol can also be contained. These dyes are generally used in concentrations of 0.001 to 0.1% by weight, based on the entire mixture.
[0085] A proporção total das substâncias auxiliares e aditivas pode perfazer de 1 a 50, preferivelmente 5 a 40% em peso, com base nos agentes. A produção dos agentes pode ocorrer por processos a frio ou quente usuais; preferivelmente trabalha-se de acordo com o método de temperatura de inversão de fase.[0085] The total proportion of auxiliary and additive substances can be from 1 to 50, preferably 5 to 40% by weight, based on the agents. The production of the agents can take place by the usual cold or hot processes; preferably it is worked according to the phase inversion temperature method.
[0086] Em uma forma de concretização preferida, as emulsões apresentam a seguinte composição: (a) cerca de 0,1 a cerca de 20% em peso, preferivelmente cerca de 1 a cerca de 15% em peso e, em particular, cerca de 2 a cerca de 10% em peso, de fatores de proteção solar, (b) cerca de 0,001 a cerca de 2,5% em peso, preferivelmente cerca de 0,005 a cerca de 2% em peso e, em particular, cerca de 0,01 a cerca de 1,5% em peso, de compostos de carnosina, (c) cerca de 1 a cerca de 30% em peso, preferivelmente cerca de 2 a cerca de 25 e, em particular, cerca de 5 a cerca de 10% em peso, de emulsificantes, (d) 0 a cerca de 50% em peso, preferivelmente cerca de 5 a cerca de 40% em peso e, em particular, cerca de 10 a cerca de 20% em peso, de veículo e (e) 0 a cerca de 50% em peso, preferivelmente cerca de 5 a cerca de 40% em peso e, em particular, cerca de 10 a cerca de 20% em peso, de substância oleosa, com a condição, de que as quantidades indicadas se complementem com água e opcionalmente com outras substâncias auxiliares e aditivas para 100% em peso.[0086] In a preferred embodiment, the emulsions have the following composition: (a) about 0.1 to about 20% by weight, preferably about 1 to about 15% by weight, and in particular about from 2 to about 10% by weight of sun protection factors, (b) about 0.001 to about 2.5% by weight, preferably about 0.005 to about 2% by weight, and in particular about 0.01 to about 1.5% by weight of carnosine compounds, (c) about 1 to about 30% by weight, preferably about 2 to about 25, and in particular about 5 to about from 10% by weight of emulsifiers, (d) 0 to about 50% by weight, preferably from about 5 to about 40% by weight, and in particular from about 10 to about 20% by weight of carrier and (e) 0 to about 50% by weight, preferably about 5 to about 40% by weight, and in particular about 10 to about 20% by weight, of oily substance, provided that the indicated amounts are topped up with water and optionally with other ras auxiliary and additive substances to 100% by weight.
[0087] Particularmente são preferidas emulsões, que apresentam a seguinte composição: (a) cerca de 1 a cerca de 15% em peso e preferivelmente cerca de 2 a cerca de 10% em peso, de fatores de proteção solar, (b) cerca de 0,005 a cerca de 2% em peso, preferivelmente cerca de 0,01 a cerca de 1,5% em peso e, em particular, cerca de 0,05 a cerca de 0,1% em peso, de compostos de carnosina, (c) cerca de 2 a cerca de 25 e preferivelmente cerca de 5 a cerca de 10% em peso, de emulsificantes, (d) 5 a cerca de 50% em peso, preferivelmente cerca de 5 a cerca de 40% em peso e, em particular, cerca de 10 a cerca de 20% em peso, de veículo e (e) 5 a cerca de 50% em peso, preferivelmente cerca de 5 a cerca de 40% em peso e, em particular, cerca de 10 a cerca de 20% em peso, de substância oleosa, com a condição, de que as quantidades indicadas se complementem opcionalmente com outras substâncias auxiliares e aditivas pra 100% em peso.[0087] Particularly preferred are emulsions, which have the following composition: (a) about 1 to about 15% by weight and preferably about 2 to about 10% by weight of sun protection factors, (b) about from 0.005 to about 2% by weight, preferably from about 0.01 to about 1.5% by weight, and in particular from about 0.05 to about 0.1% by weight, of carnosine compounds, (c) about 2 to about 25, and preferably about 5 to about 10% by weight, of emulsifiers, (d) 5 to about 50% by weight, preferably about 5 to about 40% by weight, and , in particular, about 10 to about 20% by weight of carrier and (e) 5 to about 50% by weight, preferably about 5 to about 40% by weight, and in particular about 10 to about 10 to about 50% by weight. about 20% by weight of oily substance, provided that the indicated amounts are optionally supplemented with other auxiliary substances and additives to 100% by weight.
[0088] Nas quantidades indicadas deve ser considerado, que esses se ajustam ao especialista. Esse não consideraria nem composições, que não somam 100% em peso ou que excedem.[0088] In the quantities indicated it must be considered, that these fit the specialist. This would not even consider compositions, which do not add up to 100% by weight or which exceed.
[0089] Finalmente, deve-se notar, que a invenção se refere àquelas emulsões, que são termodinamicamente estáveis e que se formam espontaneamente ou com baixa entrada de energia mecânica. Essa se estende, contudo, do mesmo modo, para emulsões, que apresentam a mesma distribuição do tamanho de gotícula e que foram produzidas por outro meio, por exemplo, através de homogeneização de alta pressão. A medição do diâmetro do tamanho de gotícula pode ocorrer por processos conhecidos pelo especialista. Os exemplos para esse fim compreendem processos suportados por laser, tais como, por exemplo, espectroscopia de correlação de fótons, difractometria a laser, processo de contagem de laser ou turbidimetria.[0089] Finally, it should be noted, that the invention relates to those emulsions, which are thermodynamically stable and which form spontaneously or with low input of mechanical energy. This extends, however, in the same way, to emulsions, which have the same droplet size distribution and which have been produced by another means, for example, through high pressure homogenization. The measurement of droplet size diameter can occur by methods known to the skilled person. Examples to this end include laser supported processes, such as, for example, photon correlation spectroscopy, laser diffractometry, laser counting process or turbidimetry.
[0090] Um outro objetivo da invenção refere-se a um processo para a produção de protetores solares em forma de emulsão, compreendendo as seguintes etapas: (i) fornecer pelo menos um fator de proteção solar UV; (ii) fornecer pelo menos um composto de carnosina; (iii) fornecer pelo menos um emulsificante (iv) misturar os componentes (a) e (b) opcionalmente com adição de veículos, substâncias oleosas e/ou outras substâncias cosméticas aditivas formando uma emulsão.[0090] Another object of the invention relates to a process for producing sunscreens in emulsion form, comprising the following steps: (i) providing at least one UV sun protection factor; (ii) providing at least one carnosine compound; (iii) providing at least one emulsifier (iv) mixing components (a) and (b) optionally with the addition of vehicles, oily substances and/or other additive cosmetic substances forming an emulsion.
[0091] Finalmente, a invenção refere-se também ao uso de compostos de carnosina da fórmula (I) como estabilizadores para emulsões e, em particular, emulsões, sendo que essas são fere usadas em quantidades na faixa de cerca de 0,001 a cerca de 2,5% em peso - com base na emulsão -.[0091] Finally, the invention also relates to the use of carnosine compounds of formula (I) as stabilizers for emulsions and, in particular, emulsions, these being used in amounts ranging from about 0.001 to about 0.001 2.5% by weight - based on emulsion -.
[0092] A menos que seja expressamente declarado, as formas de concretização mencionadas acima e as especificações de faixas preferidas referem-se também ao processo reivindicado e ao uso reivindicado. Uma repetição é, por conseguinte, desnecessária.[0092] Unless expressly stated, the above-mentioned embodiments and preferred range specifications also refer to the claimed process and claimed use. A repetition is therefore unnecessary.
[0093] A seguir, a invenção é esclarecida em detalhes com base em exemplos de concretização, contudo, sem que essa seja restrita aos mesmos. Na primeira parte são encontradas pesquisas experimentais, que atesta o caráter até agora não conhecido dos compostos de carnosina como substâncias ativas para proteger a pele contra influências ambientais. Na segunda parte é mostrado, que as carnosinas são capazes de manter as emulsões, que contêm os fatores de proteção solar UV, estáveis por períodos mais longos, também a temperaturas elevadas. Na última parte são dados, finalmente, exemplos de formulações.[0093] Next, the invention is explained in detail based on examples of embodiment, however, without being restricted thereto. In the first part, experimental research is found, which attests to the hitherto unknown character of carnosine compounds as active substances to protect the skin against environmental influences. In the second part, it is shown that carnosines are able to keep emulsions, which contain UV sun protection factors, stable for longer periods, also at elevated temperatures. In the last part, examples of formulations are finally given.
[0094] Fundamento: A enzima glicose 6 fosfato desidrogenase (G6PDH) catalisa a primeira etapa da “via das pentoses”, na qual se forma um elemento constituinte essencial do DNA, a saber, a desoxir- ribose. Neste caso, a glicose 6 fosfato (G6P) com auxílio de G6PDH é convertida em 6-fosfato gluconato (6PG). Ao mesmo tempo, a coenzi- ma NADP necessária, neste caso, é reduzida para NADPH2 que, por sua vez, pode catalisar um grande número de outras reações biológicas, tais como, por exemplo, a reciclagem de glutation ou a síntese do lipídeo. O glutation reduzido protege muitas enzimas, que dispõem de grupos SH e células contra o estresse oxidativo, tal como, por exemplo, a ação do UV. Assim, o teor de G6PDH é um parâmetro importante para a proteção celular e para a renovação da pele.[0094] Background: The enzyme glucose 6 phosphate dehydrogenase (G6PDH) catalyzes the first step of the “pentose pathway”, in which an essential constituent element of DNA, namely deoxyribose, is formed. In this case, glucose 6 phosphate (G6P) with the help of G6PDH is converted into gluconate 6-phosphate (6PG). At the same time, the coenzyme NADP required in this case is reduced to NADPH2 which, in turn, can catalyze a large number of other biological reactions, such as, for example, glutathione recycling or lipid synthesis. Reduced glutathione protects many enzymes, which dispose of SH groups and cells against oxidative stress, such as, for example, the action of UV. Thus, the G6PDH content is an important parameter for cell protection and skin renewal.
[0095] Método: A atividade da G6PDH foi determinada in vitro em fibroblastos humanos de acordo com o método enzimático de Okada, o teor de DNA, de acordo com o processo de Desaulniers. Os resultados são compilados na tabela 1. São indicados os resultados de 3 séries de medição cada com determinação tripla em % relativa, em comparação com uma amostra em branco.Tabela 1 Estimulação da atividade de G6PDH (indicada em % relativa) [0095] Method: The activity of G6PDH was determined in vitro in human fibroblasts according to the enzymatic method of Okada, the DNA content according to the process of Desaulniers. Results are compiled in Table 1. Results of 3 measurement series each with triple determination in % relative compared to a blank sample are shown.Table 1 Stimulation of G6PDH activity (indicated in % relative)
[0096] Tal como mostram os exemplos, a adição de carnosina leva a que tanto a quantidade de DNA celular, como também a G6PDH aumenta de maneira estatisticamente significativa. Esse efeito por sí só já inesperado pode ser aumentado ainda através da combinação com filtros de proteção solar UV, embora isoladamente esses não mostrem qualquer efeito.[0096] As the examples show, the addition of carnosine causes both the amount of cellular DNA and G6PDH to increase in a statistically significant way. This already unexpected effect in itself can be further enhanced by the combination with UV sun protection filters, although these alone do not show any effect.
[0097] Fundamento: A apoptose, ao contrário da necrose, é uma morte celular naturalmente direcionada de células indesejadas ou danificadas. Trata-se de um processo ativo das células (suicídio sob comando). Especialmente no envelhecimento da pele, devido a uma deficiência de fatores do crescimento na pele, ocorre uma apoptose induzida das células da pele. Nas respectivas células afetadas pela apoptose o DNA nuclear é degradado através da enzima específica endonuclease e os fragmentos de DNA são canalizadas para o citoplasma.[0097] Background: Apoptosis, unlike necrosis, is a naturally targeted cell death of unwanted or damaged cells. It is an active process of cells (suicide on command). Especially in aging skin, due to a deficiency of growth factors in the skin, induced apoptosis of skin cells occurs. In the respective cells affected by apoptosis the nuclear DNA is degraded by the specific enzyme endonuclease and the DNA fragments are channeled to the cytoplasm.
[0098] Método: É pesquisada a capacidade de carnosinas de pre venir a apoptose induzida por uma deficiência de fibroblastos humanos em células da pele humana. Esses testes foram realizados in vitro em fibroblastos humanos e queratinócitos humanos. As células humanas foram cultivadas em um meio nutritivo (DMEM = Dulbecco Minimum Essential Medium pela empresa Life Technologie Sarl) com 10% de soro fetal de vitela (da empresa Dutcher). A esse meio nutritivo foi acrescentada bromodesoxiuridina BrdU), que foi incorporada no DNA e, mais tarde, serviu para detectar os fragmentos de DNA no citoplasma. Depois de um período de incubação de dois dias, o meio nutritivo foi trocado por meio nutritivo (DMEM) sem soro fetal de vitela. A substância ativa a ser testada foi acrescentada. Para comparar, uma amostra de célula sem a substância ativa a ser testada foi incubada.[0098] Method: The ability of carnosines to prevent apoptosis induced by a deficiency of human fibroblasts in human skin cells is investigated. These tests were performed in vitro on human fibroblasts and human keratinocytes. Human cells were cultured in a nutrient medium (DMEM = Dulbecco Minimum Essential Medium by the company Life Technologie Sarl) with 10% fetal calf serum (from the Dutcher company). Bromodeoxyuridine BrdU was added to this nutrient medium, which was incorporated into the DNA and later served to detect DNA fragments in the cytoplasm. After a two-day incubation period, the nutrient medium was changed to nutrient medium (DMEM) without fetal calf serum. The active substance to be tested was added. To compare, a cell sample lacking the active substance to be tested was incubated.
[0099] Depois de um outro período de incubação de um ou dois dias a 37oC, as células foram recuperadas através de tripsinização de acordo com o método de Dunnebacke e Zitcer descrito em: Cell and tissue culture, editor: J. Paul, Churchill Livingstone, 1975, página 226. Depois da tripsinização as células foram centrifugadas e contadas. Em seguida, o teor de BrdU em fragmentos de DNA do citoplasma foi determinado com auxílio do teste ELISA (kit ELISA da empresa Roche). O teor de BrdU é uma medida para os fragmentos de DNA, que do núcleo, do núcleo celular, foram canalizados para o citoplasma. Os resultados foram baseados em um milhão de células e indicados em porcentos em comparação com o controle. Os resultados são compilados na seguinte tabela 2. Tabela 2 Número de células e teor de fragmentos de DNA [0099] After another incubation period of one or two days at 37oC, cells were recovered by trypsinization according to the Dunnebacke and Zitcer method described in: Cell and tissue culture, editor: J. Paul, Churchill Livingstone , 1975, page 226. After trypsinization the cells were centrifuged and counted. Then, the content of BrdU in DNA fragments from the cytoplasm was determined with the aid of the ELISA test (ELISA kit from Roche). The BrdU content is a measure for the DNA fragments, which from the nucleus, from the cell nucleus, have been channeled into the cytoplasm. Results were based on one million cells and reported in percent compared to control. The results are compiled in the following table 2. Table 2 Number of cells and content of DNA fragments
[00100] Os exemplos in vitro mostram, que através do uso de car- nosinas, a apoptose em culturas de células humanas e o teor de fragmentos livres de DNA no citoplasma e, com isso, o grau de DNA destruído no núcleo celular, diminuem.[00100] In vitro examples show that, through the use of carnosines, apoptosis in human cell cultures and the content of free DNA fragments in the cytoplasm and, therefore, the degree of DNA destroyed in the cell nucleus, decrease .
[00101] Fundamento: O alvo dessas pesquisas é a prova de uma atividade estimulante de carnosinas sobre a síntese das macromolécu- las dérmicas em culturas de fibroblastos humanos in vitro. A derme é constituída de células (fibroblastos e mastócitos), componentes de tecidos (colágeno e elastina) e de chamadas substâncias de base. Essas substâncias de base incluem, por exemplo, glicosaminoglicano (GAG), ácido hialurônico, sulfato de condroitina, sulfato de dermatano e glicoproteínas. Devido ao envelhecimento da pele, a ligação intermo- lecular e elasticidade da derme e, assim, a firmeza da pele, diminui. Do mesmo modo, o número de células da pele presentes, em particular, os fibroblastos, diminui no decorrer do envelhecimento da pele. As fibras de colágeno são fragmentadas no decorrer do tempo e a proporção de colágeno insolúvel para solúvel aumenta. As fibras elásticas dérmicas finas engrossam e são destruídas. A síntese de GAG (glico- saminoglicano) diminui. Todos esses processos contribuem para o envelhecimento da pele e suas manifestações, tais como rugas e falta de firmeza da pele.[00101] Background: The aim of these investigations is to prove a stimulating activity of carnosines on the synthesis of dermal macromolecules in in vitro cultures of human fibroblasts. The dermis is made up of cells (fibroblasts and mast cells), tissue components (collagen and elastin) and so-called basic substances. These base substances include, for example, glycosaminoglycan (GAG), hyaluronic acid, chondroitin sulfate, dermatan sulfate and glycoproteins. Due to skin aging, the intermolecular bonding and elasticity of the dermis, and thus the skin's firmness, decreases. Likewise, the number of skin cells present, in particular fibroblasts, decreases as the skin ages. Collagen fibers are fragmented over time and the ratio of insoluble to soluble collagen increases. The thin dermal elastic fibers thicken and are destroyed. GAG (glycosaminoglycan) synthesis decreases. All these processes contribute to skin aging and its manifestations, such as wrinkles and lack of skin firmness.
[00102] Método: O método de medição baseia-se em uma coloração de macromoléculas em uma cultura de fibroblastos humanos, que com o colágeno do tipo I forma um gel de colágeno ou fibras de rede de colágeno. Certas regiões dessas fibras são quantificadas com auxílio de reagentes de coloração na parte das macromoléculas mencionadas.[00102] Method: The measurement method is based on a staining of macromolecules in a culture of human fibroblasts, which with type I collagen form a collagen gel or collagen network fibers. Certain regions of these fibers are quantified with the aid of staining reagents in the part of the mentioned macromolecules.
[00103] Para essa finalidade, mistura-se uma suspensão de fi- broblastos humanos com uma solução de colágeno do tipo I (1-2 mg/ml). Essa mistura foi incubada por 14 dias em um meio nutritivo definido (DMEM = Dulbecco Minimum Essential Medium, empresa Life Technologie Sarl) com 0,5 ou 2% em peso, de soro fetal de vitela (FCS) a 37oC em uma atmosfera de CO2 a 5%, em placas de Petri (5 ml por placa) com adição de diversas concentrações dos extratos de plantas a serem pesquisados.[00103] For this purpose, a suspension of human fibroblasts is mixed with a solution of type I collagen (1-2 mg/ml). This mixture was incubated for 14 days in a defined nutrient medium (DMEM = Dulbecco Minimum Essential Medium, company Life Technologie Sarl) with 0.5 or 2% by weight of fetal calf serum (FCS) at 37oC in a CO2 atmosphere. at 5%, in Petri dishes (5 ml per dish) with the addition of different concentrations of plant extracts to be investigated.
[00104] A cinética da concentração do gel de colágeno foi determinada 2 a 3 vezes por semana medindo dois diâmetros perpendiculares em cada gel de colágeno com um microscópio com sistema de análise de imagem. O tamanho da área é mostrado na tabela 8 em cm2. Depois de uma incubação de 14 dias, a densidade do gel de colágeno foi determinada através de uma análise de imagem com uma fonte de luz a partir da luz visível, em que foram pesquisados de forma comparati- va diferentes tons de cinza. Trata-se de uma determinação relativa da densidade (0=claro ou branco e 1=preto), que pode ser provida sem qualquer unidade.[00104] The kinetics of collagen gel concentration was determined 2 to 3 times a week by measuring two perpendicular diameters on each collagen gel with a microscope with image analysis system. The size of the area is shown in table 8 in cm2. After an incubation of 14 days, the density of the collagen gel was determined through an image analysis with a light source from visible light, in which different shades of gray were comparatively investigated. This is a relative density determination (0=light or white and 1=black), which can be provided without any units.
[00105] Depois de um período de incubação 7 e depois de 14 dias, foram feitas biópsias (amostras de tecido) e obtidas secções histológicas do gel de colágeno com fibroblastos humanos. A síntese das ma- cromoléculas foi pesquisada e quantificada através da coloração de glicosaminoglicano com PAS-Alcian azul, por exemplo, da empresa SIGMA, de acordo com o método de coloração ácido periódico-Schiff (PAS), descrito em: Mowry RW, Anal. NY Adad. Sci. 106 Art 2, 402, 1963. A avaliação da estimulação da síntese de macromoléculas foi realizada diretamente no ambiente de fibroblastos. Essa zona é designada também como “área de perifibroblastos”.[00105] After an incubation period of 7 and after 14 days, biopsies (tissue samples) were taken and histological sections of collagen gel were obtained with human fibroblasts. Macromolecule synthesis was investigated and quantified by staining glycosaminoglycan with PAS-Alcian blue, for example, from the company SIGMA, according to the periodic acid-Schiff (PAS) staining method, described in: Mowry RW, Anal . NY Adad. Sci. 106 Art 2, 402, 1963. The assessment of the stimulation of macromolecule synthesis was performed directly in the fibroblast environment. This zone is also called the “perifibroblast area”.
[00106] Uma quantificação da secreção dos “perifibroblastos” ou da secreção de fibroblastos na periferia, foi realizada por um analisador de imagens por meio de um microscópio. Foram detectadas estruturas reativas na “área de perifibroblastos” e os diferentes tons de cinza foram determinados de forma comparativa. Neste caso, os valores dos tons de cinza foram divididos de 0 = branco até 255 = preto. Esses parâmetros são diretamente proporcionais à intensidade da síntese de macromoléculas e, assim, à proporção de GAG dos fibroblastos.[00106] A quantification of the secretion of the “perifibroblasts” or the secretion of fibroblasts in the periphery, was performed by an image analyzer by means of a microscope. Reactive structures were detected in the “perifibroblast area” and the different shades of gray were comparatively determined. In this case, the grayscale values were divided from 0 = white to 255 = black. These parameters are directly proportional to the intensity of macromolecule synthesis and, thus, to the proportion of GAG in the fibroblasts.
[00107] Na seguinte tabela 3 são mostrados os resultados dos valores desses parâmetros e são vistos diretamente como valores representativos para a atividade de síntese dos fibroblastos. A proporção dos GAGs é descrita como valor relativo dos tons de cinza.Tabela 3 Teor de GAGs nas amostras de tecido de fibroblastos humanos com colágeno. * 5% em peso, de soro fetal de vi tela (FCS)[00107] In the following table 3 the results of the values of these parameters are shown and are seen directly as representative values for the synthesis activity of fibroblasts. The proportion of GAGs is described as the relative value of shades of gray.Table 3 Content of GAGs in human fibroblast tissue samples with collagen. * 5% by weight of fetal calf serum (FCS)
[00108] A partir dos resultados da determinação da proporção de glicosaminoglicano em amostras de tecido de gel de colágeno com fibroblastos, especialmente na área de perifibroblastos, depois de um período de incubação de 14 dias, em comparação com o padrão com adição de carnosinas, pode ser reconhecido um aumento significativo da proporção de GAG. Isso aponta in vitro para uma atividade regenerativa e revitalisante de carnosinas em fibroblastos humanos.[00108] From the results of determining the proportion of glycosaminoglycan in collagen gel tissue samples with fibroblasts, especially in the perifibroblast area, after an incubation period of 14 days, compared to the standard with addition of carnosines, a significant increase in the proportion of GAG can be recognized. This points in vitro to a regenerative and revitalizing activity of carnosines in human fibroblasts.
[00109] Fundamento: A elastase é uma protease, que em estados inflamatórios é separada pelos fibroblastos e é co-responsável pela degradação de macromoléculas dérmicas, tais como, por exemplo, colágenio e elastica e, assim, pelo envelhecimento da pele.[00109] Background: Elastase is a protease, which in inflammatory states is separated by fibroblasts and is co-responsible for the degradation of dermal macromolecules, such as, for example, collagen and elastic, and thus for skin aging.
[00110] Método: Para pesquisar a eficácia do extrato de plantas pa ra inibidor a liberação de elastase, pesquisou-se a elastase pancreáti- ca (uma serina protease) e como substrato a elastina foi marcada com um substrato sintético cromogênico. O sistema foi incubado com as substâncias ativas durante 30 minutos à temperatura ambiente e, em seguida, depois da centrifugação, a densidade ótica do corante foi de- terminada a 40 nm. A quantidade de aplicação dos extratos foi de 0,3% em peso. Os resultados estão compilados na tabela 4. A indicação ocorreu relativamente a um controle como padrão (= 0%), como padrão serviu a a1-antitripsina.Tabela 4 Inibição de elastina [00110] Method: To investigate the efficacy of the plant extract to inhibit the release of elastase, pancreatic elastase (a serine protease) was researched and as a substrate, elastin was labeled with a synthetic chromogenic substrate. The system was incubated with the active substances for 30 minutes at room temperature and then, after centrifugation, the optical density of the dye was determined at 40 nm. The amount of application of the extracts was 0.3% by weight. The results are compiled in Table 4. The indication occurred relative to a control as standard (= 0%), as standard served α1-antitrypsin.Table 4 Inhibition of elastin
[00111] Os resultados evidenciam, que as carnosina são capazes de inibir a elastase e, especialmente, a elastase do pâncreas.[00111] The results show that carnosine is able to inhibit elastase and especially pancreas elastase.
[00112] Para provar, que as carnosinas inibem a glicação não en- zimática de macromoléculas, o coláageno do tipo I foi tratado com glicose e com os extratos por um período de 21 dias a 45oC. Em seguida, as suspensões foram centrifugadas e o teor das bases de Schiff no líquido sobrenadante foi determinado através de medição de fluorescência a 430 nm. Os resultados estão compilados na tabela 5. Os dados referem-se novamente ao controle como padrão (sem extrato e sem glicose).Tabela 5 Inibição da glicação de colágeno [00112] To prove that carnosines inhibit non-enzymatic glycation of macromolecules, type I collagen was treated with glucose and extracts for a period of 21 days at 45oC. Then, the suspensions were centrifuged and the content of Schiff's bases in the supernatant liquid was determined by measuring fluorescence at 430 nm. The results are compiled in Table 5. Data refer again to the control as standard (no extract and no glucose).Table 5 Inhibition of collagen glycation
[00113] Os resultados in vitro apontam para o fato, de que as car- nosinas são capazes de inibir a glicação do colágeno e, assim, retardar o processo de envelhecimento da derme através da glicação das fibras de colágeno.[00113] The in vitro results point to the fact that carnosines are able to inhibit collagen glycation and thus delay the aging process of the dermis through the glycation of collagen fibers.
[00114] Várias emulsões contendo diferentes fatores de proteção solar UV foram homogeneizadas sob alta pressão, de modo que o valor D50 sitou-se na faixa de 0,1 a 100 μm. Em seguida, as emulsões foram trasfegadas sob exclusão de ar em frascos escuros de 150 ml e, em seguida, com e sem adição de 0,2% em peso, de carnosina, foram armazenadas na estufa de secagem a 40oC por um período de 6 semanas. A avaliação ocorrer depois de 1 semana cada de armazenamento de acordo com a seguinte escala: (++) = nenhuma alteração; (+) = pequena turvação; (#) = nítida turvação; (-) = separadas.[00114] Several emulsions containing different UV sun protection factors were homogenized under high pressure, so that the D50 value was in the range of 0.1 to 100 μm. Then, the emulsions were transferred under air exclusion in 150 ml dark flasks and then, with and without addition of 0.2% by weight of carnosine, they were stored in a drying oven at 40oC for a period of 6 weeks. The evaluation takes place after 1 week each of storage according to the following scale: (++) = no change; (+) = small turbidity; (#) = clear turbidity; (-) = separated.
[00115] Os resultados estão compilados na tabela 6. Os exemplos 15 até 17 são de acordo com a invenção, os exemplos V3 até V5 servem para comparação.Tabela 6 Pesquisas de estabilidade (dados quantitativos como % em peso) [00115] The results are compiled in table 6. Examples 15 to 17 are according to the invention, examples V3 to V5 are for comparison.Table 6 Stability surveys (quantitative data as % by weight)
[00116] As emulsões de acordo com a invenção provam ser completamente estáveis por mais de 5 semanas quando armazenadas a 40oC; uma primeira turvação se realiza depois de 6 semanas. Nesse momento, todas as formulações comparativas sem adição de carnosi- na já estavam separadas. EXEMPLOS DE FORMULAÇÕES Spray de proteção solar (quantidade em % em peso) (Tabela 7) Spray de proteção solar O/W, SPE 15-20 (quantidade em % em peso) (Tabela 8) Creme de proteção solar (W/O), SPF 40 (quantidade em % em peso) (Tabela 9) Leite de proteção solar (W/O) (quantidade em % em peso) (Tabela 10) [00116] The emulsions according to the invention prove to be completely stable for more than 5 weeks when stored at 40oC; a first clouding occurs after 6 weeks. At this point, all comparative formulations without the addition of carnosine were already separated. EXAMPLES OF FORMULATIONS Sun protection spray (amount in % by weight) (Table 7) O/W sunscreen spray, SPE 15-20 (amount in % by weight) (Table 8) Sun protection cream (W/O), SPF 40 (amount in % by weight) (Table 9) Sun protection milk (W/O) (amount in % by weight) (Table 10)
Claims (15)
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PCT/EP2015/079711 WO2017101976A1 (en) | 2015-12-15 | 2015-12-15 | Preparations comprising carnosines |
PCT/EP2016/081238 WO2017102971A1 (en) | 2015-12-15 | 2016-12-15 | Emulsions having uv sunscreen factors and carnosines |
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EP0436611A4 (en) * | 1988-09-28 | 1992-03-11 | Peptide Technology Ltd | Compound and method for the retardation of collagen cross-linking |
US6720001B2 (en) * | 1999-10-18 | 2004-04-13 | Lipocine, Inc. | Emulsion compositions for polyfunctional active ingredients |
KR20020044740A (en) * | 2000-12-06 | 2002-06-19 | 강경선 | Preventive and therapeutic agents for apoptosis-related diseases which contain carnosine as a pharmaceutically active ingredient |
DE10155542A1 (en) | 2001-11-12 | 2003-05-22 | Basf Ag | Cosmetic or dermatological sunscreen preparation |
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US20030161802A1 (en) | 2002-02-05 | 2003-08-28 | Flammer Linda J. | Anti-dandruff and anti-itch compositions containing sensate and sensate enhancer-containing compounds |
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DE10245727A1 (en) * | 2002-10-01 | 2004-04-15 | Beiersdorf Ag | Sprayable W / O emulsions as aerosol |
KR20040074795A (en) * | 2003-02-19 | 2004-08-26 | 애경산업(주) | Cosmetic composition for preventing a wrinkles |
DE10308565A1 (en) * | 2003-02-25 | 2004-09-09 | Symrise Gmbh & Co. Kg | Universally applicable emulsifier type O / W based on a fully neutralized phosphoric acid ester and palm glycerides for the production of creams, milks and very low-viscosity, sprayable lotions |
US8628690B2 (en) * | 2004-02-23 | 2014-01-14 | The Texas A&M University System | Nanoemulsion compositions and methods of use thereof |
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US7776915B2 (en) | 2005-03-24 | 2010-08-17 | Tracie Martyn International, Llc | Topical formulations and methods of use |
US20090017080A1 (en) * | 2007-03-15 | 2009-01-15 | Paul Robert Tanner | Personal care kit having skin care compositions with a readily perceptible difference |
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